Carboxylic acid-modified biphenyl epoxy diacrylate

ABSTRACT

A bifunctional phenylene ether oligomer of the formula (1), obtained by oxidation polymerization of a bivalent phenol of the formula (2) and a monovalent phenol of the formula (3),
 
H O—Y   a   O—X—O   Y—O   b H   (1)
 
HO—X—OH   (2)
 
Y—OH   (3)
         wherein —X— is represented by the formula (2′),       

                         
and Y—O— is represented by the formula (3),
 
     
       
         
         
             
             
         
       
         
         
           
             R2, R3, R4, R8, R9, R10 and R11 in the formula (2′) and the formula (3′) being required not to be a hydrogen atom, and its use.

This application is a divisional of Ser. No. 11/812,892, filed Jun. 22,2007, now U.S. Pat. No. 7,388,057, which is a divisional of Ser. No.11/110,917, filed Apr. 21, 2005, now U.S. Pat. No. 7,247,682, which is adivisional of Ser. No. 10/851,290, filed May 24, 2004, now U.S. Pat. No.6,962,744, which is a divisional of Ser. No. 10/180,507, filed Jun. 27,2002, now U.S. Pat. No. 6,794,481.

FIELD OF THE INVENTION

The present invention relates to a bifunctional phenylene ether oligomer(to be sometimes referred to as “PEO” hereinafter). More specifically,it relates to a curable resin composition having a phenolic hydroxylgroup, a thermosetting functional group or the like at each terminal,its cured product, its use and a process for the production thereof.According to the present invention, there are produced a thermosettingresin or a photocurable resin and its intermediate product each of whichis suitable for use in electronics fields requiring a low dielectricconstant, a low dielectric loss tangent and high toughness and alsosuitable for various uses such as coating, bonding and molding.

BACKGROUND OF THE INVENTION

As for materials for use in an electric or electronic field, as thespeed of transmission signal increases, a low dielectric constant whichdecreases a time delay and a low dielectric loss tangent which decreasesa loss are desired for utilizing a high-frequency wave (gigahertz band).Further, higher toughness is also desired in order to inhibit theoccurrence of microcracks thought to be generated by thermal shock andsecure high reliability.

For the above demands, the use of engineering plastic such aspolyphenylene ether (PPE) is proposed. PPE has excellent high frequencyproperties. On the other hand, known problems of PPE are that it is poorin compatibility with a thermosetting resin such as an epoxy resin or acyanate resin, that it has a high melt viscosity so that moldingprocessability is poor, and that a solvent in which it is soluble islimited to an aromatic hydrocarbons solvent such as toluene, benzene orxylene and an halogenated hydrocarbon solvent such as methylene chlorideor chloroform so that workability is poor.

For improving compatibility, a method of improving compatibility byblending PPE with a different resin as a compatibilizing agent isdiscussed and the pseudo IPN structuralization of a cyanate resin isalso discussed (JP-A-11-21452, etc.). However, the problems of moldingprocessability and heat resistance have not been solved yet. Further, amethod of converting a high molecular PPE into a low molecular compoundis discussed for improving moldability. For example, there are known amethod in which a high molecular PPE and a bivalent phenol areredistributed in the presence of a radical catalyst (JP-A-9-291148,etc.) and a method in which a bivalent phenol and a monovalent phenolare subjected to oxidation polymerization (JP-B-8-011747). In each ofthe above methods, a high molecular substance is presence so that it isimpossible to obtain a bifunctional low molecular oligomer effectively.

Further, an epoxy acrylate compound has been widely used as rawmaterials for various functional high molecular materials such as aphotosensitive material, an optical material, a dental material, anelectronic material and crosslinking agents for various polymers.However, since higher performances are being required in theseapplication fields in recent years, physical properties required as afunctional high molecular material become severer increasingly. As suchphysical properties, for example, heat resistance, weather resistance,low water absorptivity, high refractive index, high fracture toughness,low dielectric constant and low dielectric loss tangent are required.Until now, these required physical properties have not been necessarilysatisfied. For example, concerning the production of a printed wiringboard, it is known that an epoxy acrylate compound is used for a photosolder resist used as a permanent mask. As a resist material like above,there are known a novolak type epoxy acrylate compound disclosed inJP-A-61-243869, a bisphenol fluorene type epoxy acrylate compounddisclosed in JP-A-3-205417 and acid-modified products of these epoxyacrylate compounds. In a use for a printed wiring board, heat resistancein an immersion in a solder bath is demanded. When the heat resistanceis insufficient, swelling or peeling off of a resist film occurs, whichcauses defectives. In compliance with an increase in the speed oftransmission signal, recently, in addition to the above-mentioned heatresistance, a lower dielectric constant which decreases a time delay anda lower dielectric loss tangent which decreases a loss are desired forutilizing a high-frequency wave (gigahertz band). However, aconventional epoxy acrylate compound is insufficient in dielectriccharacteristic corresponding to a high-frequency wave. For this reason,a novel epoxy acrylate compound which satisfies the above requirementsis demanded.

On the other hand, as a thermosetting resin, there are known apolyphenylene ether modified epoxy resin, a thermosetting typepolyphenylene ether and the like. A conventional thermosetting resin hasproblems with regard to workability, moldability, heat resistance or thelike. That is, problems are that, when a varnish is prepared by usingthe conventional thermosetting resin, a solvent is limited, and that dueto a high melt viscosity, a high multilayer formation can not be carriedout and a high temperature and a high pressure are required at a moldingtime. Further, a cyanate ester resin is known as a thermosetting resinhaving excellent dielectric characteristic and excellent moldability.However, when a cyanate ester resin alone is used, a cured product istoo hard and is fragile so that it has a problem with regard to adhesiveproperty and solder resistance. When a cyanate ester resin is used incombination with an epoxy resin, the above defects can be covered tosome extent. However, it is difficult to cope with requirements of lowerdielectric characteristics for laminates, which requirements arebecoming severer, by using a conventional cyanate ester resin incombination with a conventional epoxy resin. Further, the coexistence oflower dielectric characteristics and flexibility is difficult.

Concerning a semiconductor device, an epoxy resin composition isgenerally used for sealing electronic parts such as a semiconductor. Theabove-mentioned epoxy resin composition is composed of various epoxyresins such as a cresol novolak type epoxy resin, a bisphenol A typeepoxy resin and a biphenyl type epoxy resin, a curing agent therefor, aninorganic filler, a curing accelerator as required, a coupling agent, areleasing agent, a coloring agent and the like.

In compliance with recent requirements for a decrease in size or adecrease in thickness, the formation technique of the above electronicparts is being changed from a conventional through hole mounting method(DIP: dual inline package, etc.) to a surface mounting method (SOP:small outline package, QFP: quad flat package, etc.). In the surfacemounting method, since a semiconductor device is treated at a hightemperature (for example 210° C.˜260° C.) at a solder reflow or the likeat a mounting time, a high temperature heat is applied to the entiresemiconductor device. In this case, problems such as the occurrence ofcracks in a sealing layer formed of the above epoxy resin compositionand a large decrease in humidity resistance are apt to occur. Forexample, when a thin sealing layer having a thickness of 2.0 mm or lessis used, cracks are apt to occur at the time of a solder reflow. In viewof a further improvement in physical properties and an increase in asignal transmission speed in a chip circuit, it is demanded to carry outa sealing with a sealing layer having a lower dielectric constant.

Countermeasures against the above are proposed. One countermeasure withrespect to handling is that a semiconductor device before mounting ispackaged in a moisture-proof case. As an improvement in a sealing epoxyresin composition, for example, JP-A-1-108256 discloses a sealingmaterial containing a biphenyl type epoxy resin and JP-A-64-24825discloses a sealing material containing an epoxy resin and apolyphenylene ether type resin in combination.

Further, a (meth)acrylate compound have been widely used as rawmaterials for various functional high molecular materials such as aphotosensitive material, an optical material, a dental material, anelectronic material and crosslinking agents for various polymers.However, since higher performances are being required in theseapplication fields in recent years, physical properties required as afunctional high molecular material become severer increasingly. As suchphysical properties, for example, heat resistance, weather resistance,low absorptivity, high refractive index, high fracture toughness, lowdielectric constant and low dielectric loss tangent are required. Untilnow, these required physical properties have not been necessarilysatisfied.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a bifunctionalphenylene ether oligomer which is a resin having the excellent electriccharacteristics and toughness of PPE and improved in compatibility witha different resin and moldability and which is soluble in ageneral-purpose ketone solvent and has a PPE structure whose terminalphenolic hydroxyl groups are easy to modify, and a thermosetting resinobtained from the above oligomer.

It is another object of the present invention to provide a novel epoxyacrylate compound and a curable resin composition which have excellentheat resistance and have a low dielectric constant and a low dielectricloss tangent.

It is further another object of the present invention to provide, in aprinted wiring board material field, a thermosetting resin compositionexcellent in dielectric characteristic and also excellent in molability,heat resistance, etc., a laminate obtained by using the thermosettingresin composition and a printed wiring board obtained by thethermosetting resin composition.

It is still another object of the present invention to provide a sealingepoxy resin composition capable of giving a sealing layer which is freefrom the occurrence of cracks when it is exposed to a high temperature,such as a temperature in a solder reflow, and has a low dielectricconstant.

It is still further another object of the present invention to provide,in a printed wiring board material field, a thermosetting resincomposition which copes with the severe requirement of low dielectriccharacteristics and has flexibility, a laminate obtained by using theabove thermosetting resin composition and a printed wiring boardobtained by using the above thermosetting resin composition.

It is furthermore another object of the present invention to provide anovel (meth)acrylate compound and a curable resin composition which haveexcellent heat resistance and have a low dielectric constant and a lowdielectric loss tangent.

According to the present invention 1, there is provided a bifunctionalphenylene ether oligomer of the formula (1), obtained by oxidationpolymerization of a bivalent phenol of the formula (2) and a monovalentphenol of the formula (3),H

O—Y

_(a)

O—X—O

Y—O

_(b)H  (1)HO—X—OH  (2)Y—OH  (3)

(wherein —X— is represented by the formula (2′),

in which R2, R3, R4, R8 and R9 may be the same or different and are ahalogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, R5, R6 and R7 may be the same or different and are a hydrogenatom, a halogen atom, an alkyl group having 6 or less carbon atoms or aphenyl group,

Y—O— is represented by the formula (3),

in which R10 and R11 may be the same or different and are a halogen atomor an alkyl group having 6 or less carbon atoms or a phenyl group, R12and R13 may be the same or different and are a hydrogen atom, a halogenatom, an alkyl group having 6 or less carbon atoms or a phenyl group,

provided that Y—O— is an arrangement of one kind of structure defined bythe formula (3′) or a random arrangement of at least two kinds ofstructures defined by the formula (3′), and each of a and b is aninteger of 0 to 300, preferably 0 to 100, more preferably 0 to 50,provided that at least either a or b is not 0),

R2, R3, R4, R8, R9, R10 and R11 in the formula (2) and the formula (3)being required not to be a hydrogen atom.

According to the present invention 2, further, there is provided athermosetting resin represented by the formula (4),

wherein —X—, Y—O—, a and b are as defined in the formula (1), Z is anorganic group having one or more carbon atoms and may contain an oxygenatom, and each of c and d is an integer of 0 or 1.

According to the present invention 2, further, there is provided athermosetting resin, as a preferable thermosetting resin, according tothe above, wherein —X— in the above formula is represented by theformula (5) and Y—O— has an arrangement structure of the formula (6) orthe formula (7) or a random arrangement structure of the formula (6) andthe formula (7).

According to the present invention 3, further, there is provided anepoxy acrylate compound represented by the formula (8),

wherein R13 is a hydrogen atom or a methyl group, —X—, Y—O—, a and b areas defined in the formula (1), Z, c and d are as defined in the formula(4) and n is an integer of 0 to 10.

According to the present invention 3, further, there is provided anepoxy acrylate compound according to the above, wherein —X isrepresented by the formula (5) recited above, and Y—O— has anarrangement structure of the formula (6) recited above or the formula(7) recited above or a random arrangement structure of the formula (6)and the formula (7).

According to the present invention 3, further, there are provided anacid-modified epoxy acrylate compound of the above epoxy acrylatecompound, a curable resin composition containing these, and a curedproduct obtained by curing the above composition.

According to the present invention 4, further, there is provided anepoxy resin composition for laminates, comprising a curing agent and aphenylene ether oligomer compound having a number average molecularweight of 700 to 3,000 and having an epoxy group at each terminal,represented by the formula (9),

wherein —X—, Y—O—, a and b are as defined in the formula (1), Z, c and dare as defined in the formula (4), and n is an integer of 0 to 10.

According to the present invention 4, further, there is provided a resincomposition for laminates, wherein the above resin composition furthercontains a cyanate resin.

According to the present invention 4, further, there is providedprepreg, a laminate, or a printed wiring board obtained by using theabove epoxy resin composition for laminates.

According to the present invention 5, further, there is provided asealing epoxy resin composition containing the epoxy resin compositionrecited above and further containing as ingredients an epoxy resin andan inorganic filler.

According to the present invention 6, further, there is provided a resincomposition for laminates, containing as an ingredient a phenylene etheroligomer cyanate compound having a number average molecular weight of700 to 3,000 and having a cyanate group at each terminal, represented bythe formula (10),N≡C—O

Z

_(c)

Y—O

_(a)X

O—Y

_(b)

Z

_(d)O—C≡N  (10)

wherein —X—, Y—O—, a and b are as defined in the formula (1) and Z, cand d are as defined in the formula (4).

According to the present invention 6, further, there is provided a resincomposition for laminates according to the above, which contains thecyanate compound of the formula (10) and further contains a differentcyanate ester resin and an epoxy resin.

According to the present invention 7, further, there is provided a(meth)acrylate compound represented by the formula (11),

wherein X—, Y—O—, a and b are as defined in the formula (1), Z′ is anorganic group which have no OH group in a side chain and has one or morecarbon atoms and which may contain an oxygen atom, c and d are asdefined in the formula (4), and R15 is a hydrogen atom or a methylgroup.

According to the present invention 7, further, there is provided acurable resin composition containing the above (meth)acrylate compound.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows a GPC spectrum of a product in Comparative Example 1.

FIG. 2 shows a GPC spectrum of a product in Example 2.

FIG. 3 shows GPC spectrum changes over the passage of reaction time inExample 2.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have made diligent studies concerning abifunctional phenylene ether and found that a bifunctional phenyleneether of the formula (1) is effectively produced by oxidationpolymerization of a bivalent phenol (HO—X—OH) of the formula (2) and amonovalent phenol (Y—OH) of the formula (3) in a ketone solvent. On thebasis of the above finding, the present invention has been completed.The present invention will be explained in detail hereinafter.

The bivalent phenol of the present invention refers to a bivalent phenolwhich has a stiff biphenyl structure, —X—, expressed by the formula (2′)in which R2, R3, R4, R8 and R9 may be the same or different and are ahalogen atom, an alkyl having 6 or less carbon atoms or a phenyl group,R5, R6 and R7 may be the same or different and are a hydrogen atom, ahalogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, and each of R2, R3, R4, R8 and R9 is required not to be ahydrogen atom. The formula (2) which is represented by HO—X—OH is shownbelow.

In the formula (2), 2,3,3′,5,5′-pentamethyl-[1,1′-biphenyl]-4,4′-dioland 2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol are particularlypreferred. When a bivalent phenol having no substituent at 2-site (R4 inthe formula (2)) is used as a raw material, the oxidation rate of thebivalent phenol itself is very high so that the bivalent phenol isconverted into diphenoquinone and is precipitated from a reactionsolution.

As a result thereof, the homopolymerization of monovalent phenol of theformula (3) preferentially proceeds. The growth of a phenylene etherhaving a phenolic hydroxyl group only at one terminal proceeds till theprecipitation from a reaction solution. Therefore, a bifunctionalphenylene ether soluble in methyl ethyl ketone cannot be efficientlysynthesized. For example, as a bifunctional phenol which does not have asubstituent at a 2-site, there is3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol. When this phenol isused for synthesis, the GPC spectrum of a precipitate is shown as inFIG. 1. The generation of a polymer can be confirmed. On the other hand,there is 2,2′3,3′5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol as a bivalentphenol having a substituent at a 2-site (R2 in the formula (2′)).According to GPC spectrum variations (FIG. 2) and average molecularweight changes (FIG. 3) in a reaction where the above phenol is used,the molecular weight distribution of an obtained bifunctional phenyleneether is almost the same between the initiation of the reaction and thetermination thereof and no generation of a polymer is confirmed.Therefore, an intended bifunctional phenylene ether oligomer can beeffectively obtained.

As described above, when a bivalent phenol having substituents at 2-, 3-and 5-sites is used, there is obtained a product having a molecularweight distribution which is not expected from a conventional rawmaterial having substituents at 3- and 5-sites. Therefore, for solvingthe objects of the present invention, it is required to lower theoxidation rate of bivalent phenol itself, and the existence of asubstituent at a 2-site (R2 in the formula (2) is indispensable.

The monovalent phenol of the present invention refers to a monovalentphenol represented by the formula (3) expressed by Y—O—H.

In the formula (3), R10 and R11 may be the same or different and are ahalogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, R12 and R13 may be the same or different and are a hydrogen atom,a halogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup. In particular, it is preferred that a monovalent phenol havingsubstituents at the 2- and 6-sites is used alone or used in combinationwith a monovalent phenol having a substituent(s) at the 3-site or at the3- and 5-sites in addition to the 2- and 6-sites. More preferably, whenused alone, 2,6,-dimethylphenol is preferred, and when used incombination, 2,6,-dimethylphenol and 2,3,6-trimethylphenol arepreferred. The ratio of the monovalent phenol having a substituent atthe 3-site or substituents at the 3- and 5-sites in all the monovalentphenols, when used in combination, is preferably 70% by mole or less.When the ratio of the monovalent phenol having substituent(s) at the3-site or at the 3- and 5-sites in all the monovalent phenols is morethan 70% by mole, the above monovalent phenol is converted into acrystalline compound so that, even when the compound has a numberaverage molecular weight of approximately 1,000, it is insoluble inmethyl ethyl ketone. Further, a lower molecular oligomer is obtainedwhen 2,6-dimethylphenol is used in combination with2,3,6-trimethylphenol as compared with the case where 2,6-dimethylphenolalone is used. The reason is that the methyl group at the 3-site of2,3,6-trimethylphenol retards polymerization and therefore retards thegeneration of a polymer.

Then, the production process of the present invention 1 will beexplained. The bifunctional phenylene ether oligomer of the presentinvention 1 represented by the formula (1) is obtained by oxidationpolymerization of the bivalent phenol of the formula (2) and themonovalent phenol of the formula (3). The oxidation method includes amethod in which an oxygen gas or air is directly used. There is also anelectrode-oxidation method. Any methods may be used, and the oxidationmethod is not specially limited. In view of safety and low-costinvestment in plant and equipment, air oxidation is preferred. When theoxidation is carried out with air, there is generally selected apressure of from atmospheric pressure to 20 kg/cm².

A catalyst used when the oxidation polymerization is carried out by theuse of an oxygen gas or air, includes copper salts such as CuCl, CuBr,Cu₂SO₄, CuCl₂, CuBr₂, CuSO₄ and CuI. These may be used alone or incombination. These catalysts may be used in combination with one amineor two or more amines. The amine includes mono- and dimethylamines,mono- and diethylamines, mono- and dipropylamines, mono- anddi-n-butylamines, mono- and sec-dipropylamines, mono- anddibenzylamines, mono- and dicyclohexylamines, mono- and diethanolamines,ethylmethylamine, methylpropylamine, allylethylamine,methylcyclohexylamine, morpholine, methyl-n-butylamine,ethylisopropylamine, benzyl methyl amine, octylbenzylamine,octyl-chlorobenzylamine, methyl(phenylethyl)amine, benzylethylamine,di(chlorophenylethyl)amine, 1-methylamino-4-pentene, pyridine,methylpyridine, 4-dimethylaminopyridine and piperidine. The catalystsshall not be limited to these examples, and any other copper salts andamines may be used. In particular, as an amine, di-n-butylamine ispreferred. The use of di-n-butylamine retards the homopolymerization ofthe monovalent phenol of the formula (3) so that a polymer is hard togenerate. Therefore, there is obtained a bifunctional phenylene etheroligomer having a sharp molecular weight distribution.

Next, the solvent used in the present invention 1 will be explained. Aketone solvent and an alcohol solvent have been thought to be a poorsolvent in oxidation polymerization and used only in a limited ratio ina conventional oxidation polymerization of PPE, while these solvents maybe used in the present invention. Conventionally, this kind of reactiongenerates a polymer which is hard to solve in an organic solvent.Therefore, it has been impossible to increase the ratio of ketone oralcohol used as a reaction solvent. However, the generation product ofthe present invention 1 is only a low molecular weight oligomer, asshown in the above chart (FIG. 2), so that it is easily dissolved inketone or alcohol. Accordingly, the range of a usable solvent hasbroadened greatly. Each of the ketone solvent and the alcohol solventmay be used alone or in combination with an aromatic hydrocarbon solventsuch as toluene, benzene or xylene or a halogenated hydrocarbon solventsuch as methylene chloride, chloroform or carbon tetrachloride, each ofwhich is a conventional solvent. The ketone solvent includes acetone,methyl ethyl ketone, diethyl ketone, methyl butyl ketone and methylisobutyl ketone. The alcohol solvent includes methanol, ethanol,butanol, propanol, methyl propylene diglycol, diethylene glycol ethylether, butyl propylene glycol and propyl propylene glycol. The ketonesolvent and the alcohol solvent shall not be limited to these. Theobject of the present invention 1 is the generation of an oligomerhaving a relatively low molecular weight and a sharp peak in a molecularweight distribution, and the effect thereof is noticeably produced whenthe ketone solvent is used. Further, in view of the solubility of thebivalent phenol as a raw material, the solvent is most preferably methylethyl ketone alone or a mixed solvent containing methyl ethyl ketone.

The reaction temperature in the production process of the presentinvention 1 is not specially limited, unless it enters the explosionlimit range of a solvent used. It is preferably 25 to 50° C. Sinceoxidation polymerization is an exothermic reaction, the control of atemperature is difficult and it is hard to control a molecular weightwhen the reaction temperature is more than 50° C. When the reactiontemperature is lower than 25° C., it enters the explosion limit range sothat safety production can not be carried out.

The phenol concentrations in the production process of the presentinvention 1 will be explained. The concentration of the bivalent phenolof the formula (2) is preferably 2 to 20% by weight based on the solventto be dropwise added. When it exceeds 20% by weight, the bivalent phenolis not completely dissolved in the solvent in some cases. On the otherhand, when the above concentration is less than 2% by weight, thereaction rate of the polymerization decreases. Further, theconcentration of the monovalent phenol of the formula (3) is preferably6 to 50% by weight based on the solvent. When the concentration exceeds50% by weight, the monovalent phenol is not completely dissolved in thesolvent in some cases. On the other hand, when the above concentrationof the monovalent phenol is less than 6% by weight, the reaction rate ofthe polymerization decreases.

The molar ratio between the bivalent phenol of the formula (2) and themonovalent phenol of the formula (3) in the production process of thepresent invention 1 is preferably in the range of from 1:1 to 1:10.Particularly preferably, the above molar ratio is from 1:2 to 1:8. Sincethe homopolymerization of the monovalent phenol is not easily caused inthe above range, it is possible to control a molecular weight. When theratio between the bivalent phenol of the formula (2) and the monovalentphenol of the formula (3) is smaller than 1:2, remains of the bivalentphenol of the formula (2) increase. Further, the above ratio is largerthan 1:10, the homopolymerization of the monovalent phenol of theformula (3) occurs so that a molecular weight becomes too large and anobtained oligomer is insoluble in methyl ethyl ketone.

An equipment for the production and the production process, used in thepresent invention 1, will be explained. A copper catalyst, an amine anda solvent are placed in a longitudinally long reactor equipped with astirrer, a thermometer, an air-introducing tube and a baffleplate. Thesematerials are stirred at 40° C. and a mixed solution obtained bydissolving the bivalent phenol and the monovalent phenol in a solvent isdropwise added to the reactor with carrying out air-bubbling. Thedropwise addition time is preferably in the range of from 50 minutes to210 minutes. When the dropwise addition time is not in the above range,the variance of molecular weight distribution of an obtained oligomer islarge. Further, after the completion of the dropwise addition, it ispreferred to carry out stirring for 5 minutes to 5 hours. Even when thestirring is carried out for more than 5 hours, a further increase inmolecular weight does not happen so that the reaction should beterminated.

Next, the present invention 2 will be explained.

As shown in the present invention 1, the present inventors havesynthesized the bifunctional phenylene ether oligomer succeeding theexcellent electric characteristics and toughness of PPE (Japanese PatentApplication No. 2001-196569). For further converting the abovebifunctional phenylene ether oligomer into a thermosetting resincomposition having high activity, the present inventors have madediligent studies and as a result found that a thermosetting resincomposition of the formula (4) improved in compatibility with adifferent resin and in molding processability can be obtained bychanging terminals of the bifunctional phenylene ether oligomer, inwhich —X— is represented by the formula (2′) and Y—O— is an arrangementof one kind of structure defined by the formula (3′) or a randomarrangement of at least two kinds of structures defined by the formula(3′), to thermosetting functional groups. On the basis of the abovefinding, the present inventors have completed the present invention 2.The present invention will be explained in detail hereinafter.

The present invention is characterized in that, in an oxidative couplingor an oxidation polymerization of phenols, the oxidation rates of thephenols themselves are lowered to effectively produce a novel phenolicresin. The present invention is completed by using as a raw material acompound having a substituent introduced at 3-site in addition tosubstituents at 2- and 6-sites which have been thought to be necessaryin an oxidation polymerization reaction. Examples of the effects thereofare as follows. Concerning an oxidative coupling of 2,6-dimethylphenol,there is a study (JP-A-60-152433) in which the pH of a solution isadjusted to 8˜9 due to the presence of a by-product diphenoquinone.However, since a reaction is more stably carried out in an oxidativecoupling using 2,3,6-trimethylphenol having a substituent at the 3-site,production is effectively carried out under a high alkali condition ofpH=approximately 13 (Japanese Patent Application No. 2001-319064).Further, concerning an oxidation polymerization reaction, as shown inJapanese patent application No. 2001-196569, it becomes possible toeffectively produce the bifunctional phenylene ether oligomer bycopolymerization of, as a bivalent phenol, the before-mentioned diolobtained from 2,3,6-trimethylphenol with, as a monovalent phenol,2,6-dimethylphenol alone, 2,3,6-trimethylphenol alone or a mixture of2,6-dimethylphenol and 2,3,6-trimethylphenol. Furthermore, concerningthermosetting derivatives (cyanate compound, epoxy compound, allylcompound) derived from these phenols, it is estimated that an increasein the number of methyl groups serves to attain low dielectriccharacteristics. That is, it has been found that the presence of asubstituent at a 3-site is very important for the present invention.

The bifunctional phenylene ether oligomer which is an intermediateproduct of the present invention has a structure represented by theformula (1) in which —X— is defined by the formula (2′) and Y—O— is anarrangement of at least one kind of structure defined by the formula(3′) or a random arrangement of at least two structures defined by theformula (3′). In the formulae, R2 to R13, a and b are as defined in theformula (1) in the present invention 1. That is, it is a phenylene etheroligomer in which it is essential that R2, R3, R4, R8, R9, R10 and R11are not an hydrogen atom.

Preferably, —X— has a structure represented by the formula (5) in whichR2, R3, R4, R7, R8 and R9 are a methyl group, and R5 and R6 are ahydrogen atom and Y—O preferably has an arrangement structure of theformula (6) alone in which R10, R11 and R12 are a methyl group and R13is a hydrogen atom or the formula (7) alone in which R10 and R11 are amethyl group and R12 and R13 are a hydrogen atom, or a randomarrangement structure of the formula (6) and the formula (7).

The bifunctional phenylene ether oligomer which is an intermediateproduct in the present invention will be explained. The phenylene etheroligomer represented by the formula (1) is effectively produced byoxidatively polymerizing a bivalent phenol represented by the formula(2) with a monovalent phenol defined by the formula (3) or a mixture ofmonovalent phenols defined by the formula (3) in toluene-alcohol or aketone solvent.

As a monovalent phenol of the formula (3), particularly, there ispreferably used a monovalent phenol having substituents at 2- and6-sites alone or in combination with a monovalent phenol havingsubstituent(s) at a 3-site or at 3- and 5-sites in addition to 2- and6-sites. More preferably, when the monovalent phenol having substituentsat 2- and 6-sites is used alone, 2,6-dimethylphenol or2,3,6-trimethylphenol is preferred. When used in combination,2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred.

The thermosetting phenylene ether oligomer compound of the presentinvention is represented by the formula (4). That is, —X— is representedby the formula (2′) and Y—O— is an arrangement of one kind of structuredefined by the formula (3′) or a random arrangement of at least twokinds of structures defined by the formula (3′). X, Y, a and b are asdefined in the formula (1). Z is an organic group having at least onecarbon atom, which organic group may contain an oxygen atom. Each of cand d is an integer of 0 or 1.

At the Z site, an organic group which has at least one carbon atom andmay contain an oxygen atom can be located. Examples thereof include—(—CH₂—)—, —(CH₂—CH₂)—, and —(—CH₂—Ar—O—)—. The above organic groupshall not be limited to these examples. The method for addition includesa method in which the organic groups are directly added to theintermediate product represented by the formula (1) and a method using ahalide having a long carbon chain at a derivative synthesis time. Themethod shall not be limited to these methods.

For convenience sake, the following explanations will be done on thebasis of a derivative from intermediate product represented by theformula (1) which is the simplest structure. The bifunctional phenyleneether oligomer of the formula (1) formula (1) is used as an intermediateproduct for producing the thermosetting phenylene ether oligomercompound. The bifunctional phenylene ether oligomer may be used in theform of a powder separated from a reaction solution or in the form of asolution thereof in a reaction solution.

An example of the process for producing the cyanate compound of thepresent invention will be explained. The cyanate compound is synthesizedby reacting the above bifunctional compound having phenolic hydroxylgroups at both terminals, represented by the formula (1), as anintermediate product, with cyanogen halide such as cyanogen chloride orcyanogen bromide in the presence of a base in dehydrohalogenation.

Typical examples of the base include tertiary amines such astrimethylamine, triethylamine, tripropylamine, dimethylaniline andpyridine, sodium hydroxide, potassium hydroxide, sodium methoxide,sodium ethoxide, calcium hydroxide, sodium carbonate, potassiumcarbonate and sodium bicarbonate. The base shall not be limited tothese.

Although not specially limited, typical examples of a solvent for thereaction includes toluene, xylene, chloroform, methylene chloride,carbon tetrachloride, chlorobenzene, nitrobenzene, nitromethane,acetone, methyl ethyl ketone, tetrahydrofuran and dioxane.

When cyanogen chloride is used, the reaction temperature is preferablybetween −30° C. and +13° C. (boiling point). When cyanogen bromide isused, it is preferably between −30° C. and +65° C.

An example of the production process for the epoxy compound of thepresent invention will be explained. The epoxy compound is synthesizedby reacting the above bifunctional compound having phenolic hydroxylgroups at both terminals, represented by the formula (1), as anintermediate product, with a halogenated glycidyl such asepichlorohydrin in the presence of a base in dehydrohalogenation.

Typical examples of the base include sodium hydroxide, potassiumhydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodiumcarbonate, potassium carbonate and sodium bicarbonate. The base shallnot be limited to these.

The reaction temperature is preferably between −10° C. and 110° C.

An example of the production process for the allyl compound of thepresent invention will be explained. The allyl compound is synthesizedby reacting the above bifunctional compound having phenolic hydroxylgroups at both terminals, represented by the formula (1), as anintermediate product, with an allyl halide such as allyl bromide orallyl chloride, or 4-bromo-1-butene having a long carbon chain in thepresence of a phase transfer catalyst under a base condition indehydrohalogenation.

Typical examples of the phase transfer catalyst include tertiary aminessuch as trimethylamine and tetramethylethylenediamine, quaternaryammonium salts such as tetrabutylammonium chloride, tetrabutylammoniumbromide, tetrabutylammonium iodide, benzyltri-n-butylammonium chloride,benzyltri-n-butylammonium bromide and benzyl-n-butylammonium iodide andquaternary phosphonium salts. The phase transfer catalyst shall not belimited to these.

Typical examples of the base include sodium hydroxide, potassiumhydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodiumcarbonate, potassium carbonate and sodium bicarbonate. The base shallnot be limited to these.

The reaction temperature is preferably between −10° C. and 60° C.

The thermosetting phenylene ether oligomer compound of the presentinvention can be cured alone or it can be cured as a resin compositionfurther containing cyanate compounds, epoxy compounds, polymerizablecompounds and/or catalysts.

Any known curing methods can be employed for curing the thermosettingphenylene ether oligomer compound. Examples of the above cyanatecompounds include m- or p-phenylenebiscyanate, 1,3,5-tricyanatebenzene,4,4′-dicyanatobiphenyl, 3,3′5,5′-tetramethyl-4,4′-dicyanatebiphenyl,2,3,3′,5,5′-pentamethyl-4,4′-dicyanatebiphenyl,2,2′3,3′,5,5′-hexamethyl-4,4′-dicyanatebiphenyl,bis(4-cyanatephenyl)methane,1-(2,3,5-trimethyl-4-cyanatephenyl)-1-(3,5,-dimethyl-4-cyanatephenyl)methane,bis(2,3,5-trimethyl-4-dicyanatephenyl)methane,1,1-bis(4-cyanatephenyl)ethane,1-(2,3,5-trimethyl-4-cyanatephenyl)-1-(3,5,-dimethyl-4-cyanatephenyl)ethane,1,1-bis(2,3,5-trimethyl-4-dicyanatephenyl)ethane,2,2-bis(4-cyanatephenyl)propane,2-(2,3,5-trimethyl-4-cyanatephenyl)-2-(3,5,-dimethyl-4-cyanatephenyl)propane,2,2-bis(2,3,5-trimethyl-4-dicyanatephenyl)propane,bis(4-cyanatephenyl)ether, bis(4-cyanatephenyl)sulfone,bis(4-cyanatephenyl)sulfide, 4,4′-dicyanatebenzophenone, andtris(4-cyanatephenyl)methane. That is, the cyanate compounds arebiphenols to which an aromatic ring having a cyanate group directlybonds, bis or polycyanate compounds to which an aromatic ring having acyanate group bonds at a crosslinking portion, prepolymers of thesecyanate compounds, prepolymers of these cyanate compounds with diamines,and a cyanate-group-containing novolak type phenolic resin derived froma novolak resin which is a reaction product between phenols such asphenol and o-cresol and formaldehyde. These cyanate compounds may beused alone or in combination.

The above-mentioned prepolymers of the cyanate ester compound will beexplained. A polyfunctional cyanate ester compound having at least twocyanate groups per molecule is polymerized by forming a triazine ring bytrimerization of cyanate groups. A substance having a molecular weightof 200 to 6,000 is used as a prepolymer. The above prepolymers can beobtained by polymerizing the above polyfunctional cyanate ester compoundmonomers in the presence of a catalyst selected from acids such asmineral acids and Lewis acids; bases such as sodium alkoxide andtertiary amines; or salts such as sodium carbonate. The prepolymerspartially contain monomers and have the form of a mixture of a monomerand a polymer, and these prepolymers are preferably used when a curedproduct is produced.

The polymerizable compounds include bismaleimide, an epoxy resin and thelike. These may be used as a mixture thereof.

Examples of the bismaleimide includes N,N′-diphenylmethanebismaleimide,N,N′-phenylenebismaleimide, N,N′-diphenyletherbismaleimide,N,N′-dicyclohexylmethanebismaleimide, N,N′-xylenebismaleimide,N,N′-diphenylsulfonebismaleimide, N,N′-tolylenebismaleimide,N,N′-xylylene bismaleimide, N,N′-diphenylcyclohexane bismaleimide,N,N′-dichloro-diphenylmethane bismaleimide, N,N′-diphenylcyclohexanebismaleimide, N,N′-diphenylmethane bismethylmaleimide,N,N′-diphenyletherbismethylmaleimide,N,N′-diphenylsulfonebismethylmaleimide, N,N′-ethylenebismaleimide,N,N′-hexamethylenebismethylmaleimide, prepolymers of theseN,N′-bismaleimide compounds, prepolymers of these bismaleimide compoundswith diamines, and maleimide-modified compounds ormethylmaleimide-modified compounds of aniline-formalin polycondensates.

Examples of the above epoxy resin include biphenol and a resin obtainedby substituting at least one site of the 2-, 2′-, 3-, 3′-, 5- and5′-sites of biphenol with a halogen atom, an alkyl group having 6 orless carbon atoms or a phenyl group; bisphenol A and a resin obtained bysubstituting at least one site of the 2-site, the 3-site and the 5-siteof bisphenol A with a halogen atom, an alkyl group having 6 or lesscarbon atoms or a phenyl group; bisphenol F and a resin obtained bysubstituting at least one site of the 2-site, the 3-site and the 5-siteof bisphenol F with a halogen atom, an alkyl group having 6 or lesscarbon atoms or a phenyl group; glycidyl ether compounds derived frombivalent or at least trivalent phenols such as hydroquinon, resorcin,tris-4-(hydroxyphenyl)methane and1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; a novolak type epoxy resinderived from a novolak resin which is a reaction product between phenolssuch as phenol and o-cresol and formaldehyde; amine type epoxy resinsderived from aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol,6-amino-m-cresol, 4,4′-diaminodiphenylmethane,3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylether,3,4′-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene,1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane,p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine,2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine,1,4-cyclohexane-bis(methylamine),5-amino-1-(4′-aminophenyl)-1,3,3-trimethylindane,6-amino-1-(4′-aminophenyl)-1,3,3-trimethylindane and the like; glycidylester compounds derived from aromatic carboxylic acids such asp-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalicacid; hydantoin type epoxy resins derived from 5,5-dimethylhydantoin andthe like; alicyclic epoxy resins such as2,2-bis(3,4-epoxycyclohexyl)propane,2,2-bis[4-(2,3-epoxypropyl)cyclohexyl)propane, vinylcyclohexenedioxideand 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate;triglycidyl isocyanurate, and 2,3,6-triglycidoxy-S-triazine. These epoxyresins may be used alone or in combination.

The above resin composition may contain a curing agent corresponding toeach of the ingredients. When the epoxy compound of the presentinvention is used or the resin composition contains the epoxy resin in aconstitution, there may be used, as a curing agent, dicyandiamide,tetramethylguanidine, an aromatic amine, a phenol novolak resin, acresol novolak resin, acid anhydride, and various aliphatic andalicyclic amines. In this case, the curing agents may be used alone orin combination. As an aromatic amine, the above aromatic diamines aretypical. As a curing agent used when the resin composition contains thecyanate compound or bismaleimide, the above aromatic diamines andalicyclic diamines are typical. Each of the curing agents may beincorporated in the resin composition in the form of the curing agentalone or may be incorporated in the resin composition in the form of aprepolymer of an ingredient to which each curing agent corresponds.

The resin composition can be thermally cured in a comparatively shorttime without containing a catalyst. However, according to the use of acatalyst, a molding temperature can be decreased and the curing time canbe shortened. As such a catalyst, there may be used amines such asN,N-dimethylaniline, triethylenediamine and tri-n-butylamine, imidazolessuch as 2-methylimidazole and 2-ethyl-4-methylimidazole, phenols such asphenol and resorcin, organometallic salts such as cobalt naphthenate,lead stearate, tin oleate, tin octylate, zinc octylate and titaniumbutyrate, chlorides such as aluminum chloride, tin chloride and zincchloride, and chelate metals. These catalyst may be used alone or incombination.

The above resin composition may contain an extending agent, a filler(containing organic and inorganic fillers), a reinforcing agent or apigment as required. Examples of these include silica, calciumcarbonate, antimony trioxide, kaoline, titanium dioxide, zinc oxide,mica, barite, carbon black, polyethylene powder, polypropylene powder,glass powder, aluminium powder, iron powder, copper powder, glass fiber,carbon fiber, alumina fiber, asbestos fiber, aramid fiber, glass wovenfabric, glass unwoven fabric, aramid unwoven fabric and liquid crystalpolyester unwoven fabric. These may be used alone or in combination.

Further, the resin composition containing these is used for molding,lamination, an adhesive or a composite material such as a copper-cladlaminate. Particularly, when the cyanate compound alone, the epoxycompound alone or a combination of the cyanate compound and the epoxycompound is used, typical examples of uses are prepreg obtained bysemi-curing the resin and a laminate obtained by curing the aboveprepreg. Further, when the epoxy compound is used, a typical example isa use for a semiconductor sealing material.

The present invention 3 is directed to an epoxy acrylate compoundrepresented by the formula (8),

wherein R13 is a hydrogen atom or a methyl group, —X—, Y—O—, a and b areas defined in the formula (1), Z, c and d are as defined in the formula(4), and n is an integer of 0 to 10.

Further, the present invention relates to an acid-modified epoxyacrylate compound obtained by further reacting the epoxy acrylatecompound of the formula (8) with a carboxylic acid or its anhydride.Further, the present invention relates to a curable resin compositioncontaining the above epoxyacrylate compound and/or the aboveacid-modified epoxy acrylate compound and further relates to a curedproduct obtained by curing the above curable resin composition.

As for a reaction method, the epoxy acrylate compound of the formula (8)is preferably produced according to a known method, for example a methoddisclosed in JP-B-44-31472 or JP-B-45-1465. That is, typically, forexample, the epoxy acrylate compound of the formula (8) can be obtainedby reacting an epoxy compound represented by the formula (9) with anacrylic acid, a methacrylic acid or a mixture of an acrylic acid and amethacrylic acid. The epoxy compound of the formula (9) is produced by,for example, the method disclosed in Japanese Patent Application No.2001-353194.

When the epoxy acrylate compound of the formula (8) in the presentinvention 3 is produced, the amount of the acrylic acid, the methacrylicacid or the mixture of these based on the epoxy resin of the formula (9)is not specially limited. Preferably, the amount of the acrylic acid,the methacrylic acid or the mixture of these per 1 chemical equivalentof an epoxy group of the epoxy compound composition is 0.1 to 5 chemicalequivalents, more preferably 0.3 to 3 chemical equivalents.

In the reaction, it is preferable to add a diluent. Examples of thediluent include alcohols such as methanol, ethanol, propanol, butanol,ethylene glycol, methyl cellosolve, ethylcellosolve, dipropylene glycolmonomethyl ether and diethylene glycol monomethyl ether, esters such asmethyl cellosolve acetate, ethylcellosolve acetate, dipropylene glycolmonomethyl ether acetate, diethylene glycol monomethyl ether acetate anddiethylene glycol monoethyl ether acetate, ketone solvents such asmethyl ethyl ketone and methyl isobutyl ketone, and aromatic compoundssuch as benzene, toluene, xylene, chlorobenzene, dichlorobenzene andsolvent naphtha.

Further, it is preferable to use a catalyst for promoting the reaction.Preferable concrete examples of the catalyst include amines such astriethylamine, dimethylbutyl amine and tri-n-butyl amine, quaternaryammonium salts such as tetramethylammonium salt, tetraethylammoniumsalt, tetrabutylammonium salt and benzyltrimethylammonium salt,quaternary phosphonium salts, phosphines such as triphenylphosphine, andimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. Theamount of the catalyst based on a mixture of reaction raw materials ispreferably 0.1 to 10% by weight, more preferably 0.2 to 3% by weight.Further, it is preferred to use a polymerization inhibitor forpreventing a polymerization during the reaction. Examples of thepolymerization inhibitor include hydroquinone, methyl hydroquinone,hydroquinone monomethyl ether, 4-methylquinoline and phenothiazine.Further, for inhibiting a polymerization reaction due to unsaturatedbonds, the reaction can be carried out under a flow of air or the likeaccording to circumstances. In this case, an antioxidant such as2,6-di-t-butyl-4-methylphenol may be used for preventing an oxidationreaction due to the air.

Although the reaction temperature varies depending upon the catalyst,preferred is a temperature at which the reaction of the epoxy compoundof the formula (9) with the acrylic acid or the methacrylic acidadvances and no thermal polymerizations of raw materials, anintermediate product and a generation product occur. More preferably,the reaction temperature is 60° C. to 150° C., particularly preferably70° C. to 130° C. Although the reaction time depends on the reactiontemperature, it is preferably 1 to 15 hours. After the completion of thereaction, an excess (meth)acrylic acid and an excess diluent may beremoved by distillation or other methods, or these materials can be usedwithout removing.

Next, the acid-modified epoxy acrylate compound of the present invention3 will be explained. The acid-modified epoxy acrylate compound of thepresent invention is produced by reacting the above epoxy acrylatecompound obtained from the epoxy compound of the formula (9) and acrylicacid, methacrylic acid or a mixture of these, with a carboxylic acid orits anhydride. The carboxylic acid is a monovalent or polyvalentcarboxylic acid, and it is preferably a monovalent or polyvalentaliphatic carboxylic acid or a monovalent or polyvalent aromaticcarboxylic acid.

Examples of the carboxylic acid or its anhydride include maleic acid,succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid,hexahydrophthalic acid, methyltetrahydrophthalic acid,methylhexahydrophthalic acid, chlorendic acid, methyl nadic acid,trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid,3,3′4,4′-biphenyl tetracarboxylic acid, cyclohexane tetracarboxylicacid, butane tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylicacid, 3,3′4,4′-diphenyl sulfone tetracarboxylic acid, 4,4′-oxydiphthalicacid, cyclopentane tetracarboxylic acid, and anhydrides of these. Thecarboxylic acid or its anhydride shall not be limited to these examples.The amount of the carboxylic acid or its anhydride per 1 chemicalequivalent of a hydroxyl group in the above epoxy acrylate compound is0.01 to 1.2 chemical equivalents, preferably 0.05 to 1 chemicalequivalent.

At the time of the reaction, various known esterification catalysts, adiluent mentioned above, and the like may be further added as required.Although the reaction temperature is not specially limited, preferred isa temperature at which no thermal polymerization of the epoxyacrylatecompound, etc., as a raw material, occurs. It is preferably 60° C. to130° C. Although the reaction time depends on the reaction temperature,it is preferably 1 to 80 hours.

After the reaction, the acid-modified epoxy acrylate compound of thepresent invention 3 can be separated by a known method such asdistillation. Further, the acid-modified epoxy acrylate compound of thepresent invention may contain an epoxy group in a molecule. That is, asdescribed before, when the amount of the acrylic acid, the methacrylicacid of the mixture of these based on the epoxy compound is adjusted toa desired amount within the above range, an unreacted epoxy group isleft in the obtained epoxy acrylate compound. The thus-obtained epoxyacrylate compound is further acid-modified, whereby an acid-modifiedepoxy acrylate compound having an epoxy group is obtained. The acidvalue of the acid-modified epoxy acrylate compound can be properlyadjusted as required. It is preferably 20 to 200 mg KOH/g, morepreferably 30 to 150 mg KOH/g.

Then, the curable resin composition of the present invention 3 will beexplained. The curable resin composition is characterized in that itcontains the above epoxy acrylate compound and/or the acid-modifiedepoxy acrylate compound of the present invention. The curable resincomposition of the present invention 3 may contain a known epoxy resin,an oxetane resin, a compound having an ethylenic unsaturated compound, aphotopolymerization initiator and/or a thermal polymerization initiator,a photosensitizer and the like. As the epoxy acrylate compound and/orthe acid-modified epoxy acrylate compound of the present invention 3,the above reaction products may be used as they are.

The epoxy resin can be selected from generally known epoxy resins.Examples of the epoxy resin include a bisphenol A type epoxy resin, abisphenol F type epoxy resin, a biphenyl type epoxy resin, a phenolnovolak type epoxy resin, a cresol novolak type epoxy resin, a xylenenovolak type epoxy resin, triglycidyl isocyanurate, an alicyclic epoxyresin, a dicyclopentadiene novolak type epoxy resin, a biphenyl novolaktype epoxy resin, epoxy resins having a PPE structure disclosed inJapanese patent application Nos. 2001-353194 and 2002-018508, andflame-retardant epoxy resins obtained by brominating any one of theseepoxy resins. These epoxy resins may be used alone or in combination.

The oxetane resin can be selected from generally known oxetane resins.Examples of the oxetane resin include alkyl oxetanes such as oxetane,2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane and3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane,3,3′-di(trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane,3,3-bis(chrolomethyl)oxetane, OXT-101 (trade name, supplied by TOAGOSEICo., Ltd.) and OXT-121 (trade name, supplied by TOAGOSEI Co., Ltd.).These oxetane resins may be used alone or in combination.

When the epoxy resin and/or the oxetane resin are used in the curableresin composition of the present invention 3, an epoxy resin curingagent and/or an oxetane resin curing agent may be used. The epoxy resincuring agent is selected from generally known curing agent. Examples ofthe epoxy resin curing agent include imidazoles such as2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,2-phenyl-4,5-dihydroxymethylimidazole,2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such asdicyandiamide, benzyldimethylamine and 4-methyl-N,N-dimethylbenzylamine;and phosphine compounds such as phosphonium compounds. The oxetane resincuring agent can be selected from known cationic polymerizationinitiator. Commercially available examples include SAN-AID SI-60L,SAN-AID SI-80L, SAN-AID SI-100L (supplied by Sanshin Chemical IndustryCo., Ltd.), CI-2064 (supplied by Nippon Soda Co., Ltd.), IRGACURE 261(supplied by Ciba Specialty Chemicals), ADEKAOPTMER SP-170, ADEKAOPTMERSP-150, (supplied by Asahi Denka Kogyo K.K.), and CYRACURE UVI-6990(supplied by Union Carbide Corporation). A cationic polymerizationinitiator may be used as an epoxy resin curing agent. These curingagents may be used alone or in combination.

The compound having an ethylenic unsaturated group can be selected fromgenerally known compounds having an ethylenic unsaturated group.Examples thereof include (meth)acrylates of monohydric and polyhydricalcohols such as 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, polypropylene glycol di(meth)acrylate,trimethylol propane di(meth)acrylate, trimethylol propanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate anddipentaerythritol hexa(meth)acrylate, and epoxy acrylates such as abisphenol A type epoxy acrylate and a bisphenol F type epoxy acrylate.These compounds having an ethylenic unsaturated group may be used aloneor in combination.

The photopolymerization initiator can be selected from generally knownphotopolymerization initiators. Examples of the photopolymerizationinitiator include α-diketones such as benzyl and diacetyl, acyloinethers such as benzoyl ethyl ether and benzoin isopropyl ether,thioxanthones such as thioxanthone, 2,4-diethylthioxanthone and2-isopropylthioxanthone, benzophenones such as benzophenone and4,4′-bis(dimethylamino)benzophenone, acetophenones such as acetophenone,2,2′-dimethoxy-2-phenylacetophenone and β-methoxy acetophenone, andaminoacetophenones such as2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one and2-benzyl-2-dimethylamino-1-(−4-morpholinophenyl)-butanone-1. Thesephotopolymerization initiators are used alone or in combination.

Further, the photopolymerization initiator may be used in combinationwith one kind of or at least two kinds of known photosensitizer(s).Examples of the photosensitizer include N,N-dimethylaminoethylbenzoate,N,N-dimethylaminoisoamylbenzoate, triethanolamine and triethylamine.

The thermal polymerization initiator may be selected from generallyknown thermal polymerization initiators. Examples thereof includeperoxides such as benzoyl peroxide, p-chlorobenzoyl peroxide,di-t-butylperoxide, diisopropyl peroxy carbonate anddi-2-ethylhexylperoxycarbonate, and azo compounds such asazobisisobutylonitrile.

Further, when the curable resin composition of the present invention 3is produced, there may be added a known additive such as an inorganicfiller, a color pigment, an antifoamer, a surface conditioner, a flameretardant, an ultraviolet absorber, an antioxidant, a polymerizationinhibitor or a flow regulator, as required. Examples of the inorganicfiller includes silicas such as natural silica, fused silica andamorphous silica, white carbon, titanium white, aerosil, alumina, talc,natural mica, synthetic mica, kaolin, clay, aluminum hydroxide, bariumsulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass andM-glass G20. The thus-obtained curable resin composition is suitable forvarious uses such as a solder resist composition, buildup wiring boardmaterials, insulating coatings, adhesives, printing inks and coatingmaterials.

The cured product of the present invention 3 can be obtained by curingthe curable resin composition of the present invention, obtained by theabove method, according to a known curing method such as a method usingan electron beam, ultraviolet light or heat. When ultraviolet light isused for the curing, there may be used a low-pressure mercury lamp, anintermediate-pressure mercury lamp, a high-pressure mercury lamp, anultrahigh-pressure mercury lamp, a xenon lamp and a metal halide lamp asa light source for ultraviolet light.

The epoxy resin composition of the present invention 4 is athermosetting resin composition excellent in dielectric characteristics,moldability and heat resistance. It contains as a main ingredient aphenylene ether oligomer epoxy compound having an epoxy group at eachterminal, represented by the formula (9), and it is suitable for use asan ingredient for an epoxy resin composition for laminates.

That is, the present invention 4 provides an epoxy resin composition forlaminates, containing as ingredients a phenylene ether oligomer epoxycompound having a number average molecular weight of 700 to 3,000 andhaving an epoxy group at each terminal, represented by the formula (9),and a curing agent,

wherein —X—, Y—O—, a and b are as defined in the formula (1), Z, c and dare as defined in the formula (4), and n is an integer of 0 to 10,preferably 0 to 6.

The present invention 4 further provides an epoxy resin composition forlaminates, which composition contains a phenylene ether oligomer epoxycompound having a number average molecular weight of 700 to 3,000 andhaving an epoxy group at each terminal, represented by the formula (9),and a cyanate ester resin as ingredients.

In the present invention 4, concerning the above epoxy resin compositioncontaining the epoxy compound and the curing agent, the phenylene etheroligomer epoxy compound having an epoxy resin at each terminalrepresented by the formula (9) preferably has a structure in which atleast R2, R3, R4, R8 and R9 in the formula (2′), which represents —X—,are a methyl group, further at least one of R5, R6 and R7 in the formula(2′) may be a methyl group and Y—O— is an arrangement of the formula (6)or the formula (7) or a random arrangement of the formula (6) and theformula (7)

Since the epoxy resin composition of the present invention 4 containsthe phenylene ether oligomer epoxy compound having an epoxy group ateach terminal represented by the formula (9), it has a low dielectricconstant and excellent flexibility and the melt viscosity thereof can bedecreased. When the melt viscosity of the resin composition is low, theembeddability of the resin is good at a laminate-molding time and novoids occur so that moldability is excellent.

The phenylene ether oligomer epoxy compound, represented by the formula(9), having an epoxy group at each terminal (to be referred to as“bifunctional PEO-2Ep” hereinafter) used in the present invention 4 willbe explained.

The above bifunctional PEO-2Ep is obtained by reacting the phenyleneether oligomer (to be referred to as “bifunctional PEO” hereinafter) ofthe formula (1) obtained by oxidative copolymerization of the bivalentphenol and the monovalent phenol, with a halogenated glycidyl such asepichlorohydrin in the presence of a base in dehydrohalogenation. It maybe used as a powder separated from a reaction liquid or as a solutionthereof in a reaction liquid.

An example of the process for producing the bifunctional PEO-2Ep of thepresent invention 4 will be shown. The above compound having phenolichydroxyl groups at both terminals, represented by the formula (1), isreacted with a halogenated glycidyl such as epichlorohydrin in thepresence of a base in dehydrohalogenation, whereby the bifunctionalPEO-2Ep is synthesized.

The number average molecular weight of the obtained bifunctional PEO-2Epis limited in the range of from 700 to 3,000. When the above numberaverage molecular weight exceeds 3,000, the melt viscosity of the resincomposition increases. When it is smaller than 700, mechanical strengthor heat resistance is decreased. The above bifunctional PEO-2Ep has alow melt viscosity so that its flowability is high. It is excellent incompatibility with a different resin. Further, since it has epoxy groupsat both terminals, the resin composition containing it has good adhesiveproperties. As a result thereof, when the resin composition is exposedto a high temperature at soldering or the like after moistureabsorption, the occurrence of swelling is prevented. Further, since apolyphenylene ether resin is a material having low dielectriccharacteristics, there can be provided a laminate having low dielectriccharacteristics.

The curing agent, which is an ingredient of the epoxy resin compositionfor laminates provided by the present invention 4, includes generallyused curing agents such as amine type curing agents typified by primaryamine and secondary amine, phenol type curing agents typified bybisphenol A and phenol novolak, acid anhydride type curing agents, andcyanate-ester type curing agents. These curing agents may be used aloneor in combination.

The bifunctional PEO-2Ep composition of the present invention can beused in combination with various resins according to a purpose or use.Specific examples of the resins include various epoxy resins; modifiedepoxy resins, oxetane resins, acrylates, methacrylates; polyallylcompounds such as diallyl benzene and diallyl terephthalate; vinylcompounds such as N-vinyl-2-pyrolidone and divinyl benzene;polymerizable double-bond-containing monomers such as unsaturatedpolyester; polyfunctional maleimides; polyimides; rubbers such aspolybutadiene, thermoplastic resins such as polyethylene andpolystyrene; engineering plastics such as a ABS resin and polycarbonate;and a cyanate ester resin. The above resins shall not be limited tothese resins.

Further, the resin composition may contain various additives such as aknown inorganic or organic filler, a dye, a pigment, a thickener, alubricant, an antifoamer, a coupling agent, a photosensitizer, anultraviolet absorber and a flame retardant, as required.

Examples of the cyanate ester compound used in the present invention 4include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-,1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene,1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl,bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane,2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether,bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone,tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate,4,4′-dicyanato-3,3′,5,5′-tetramethylbiphenyl,4,4′-dicyanato-2,2′,3,3′,5,5′-hexamethylbiphenyl, and cyanates obtainedby a reaction of novolak with cyanogen halide.

Although the composition of the present invention 4 undergoes curingitself under heat, a heat-curing catalyst can be incorporated in thecomposition for increasing the curing rate and improving workability andeconomic efficiency. There may be used a generally known heat-curingcatalyst as a heat-curing catalyst for the resin to be used incombination.

A copper-clad laminate obtained by using the bifunctional PEO-2Epcomposition of the present invention 4 is particularly suitably used fora printed wiring board which is required to have low dielectriccharacteristics. The copper-clad laminate of the present invention 4 canbe produced by a general method. That is, it is a method in which a basematerial is impregnated with a resin varnish which is a solution of athermosetting resin composition in an organic solvent, the base materialis heat-treated to obtain prepreg, and then the prepreg and a copperfoil are laminated and molded under heat to obtain a copper-cladlaminate. However, the production method of the copper-clad laminate ofthe present invention shall not be limited to this method.

The organic solvent includes acetone, methyl ethyl ketone, ethyleneglycol monomethyl ether acetate, propylene glycol dimethyl ether,toluene, xylene, tetrahydrofuran and N,N-dimethylformamide. The solventis not specially limited and various organic solvents may be used. Thesesolvents may be used alone or in combination. The base material to beimpregnated with the resin varnish includes all base materials used fora thermosetting resin laminate. Example thereof includes inorganic basematerials such as a glass cloth and a glass unwoven fabric; and organicbase materials such as a polyamide unwoven fabric and a liquidcrystalline polyester unwoven fabric. For utilizing the low dielectriccharacteristics of the present invention, it is more effective to use abase material having excellent dielectric characteristics such as Dglass cloth or NE glass cloth.

The heat-treatment of the prepreg is properly selected depending uponthe kinds and the amounts of the solvent used, the resin constitution,the catalyst added and other additives, while it is generally carriedout at a temperature of 100 to 250° C. for 3 to 30 minutes. The methodof laminating and heating the prepreg and the copper foil variesdepending upon the kind of the prepreg and the form of the copper foil.Generally, these materials are preferably thermally press-molded invacuum at a temperature of 170 to 230° C. under a pressure of 10 to 30kg/cm² for 40 to 120 minutes.

The present invention 5 provides a sealing epoxy resin compositioncontaining as ingredients an epoxy resin, a curing agent, an inorganicfiller and a phenylene ether oligomer compound having a number averagemolecular weight of 700 to 3,000 and having an epoxy group at eachterminal, represented by the formula (9).

According to the present invention 5, there is provided a sealing epoxyresin composition capable of giving a sealing layer which is free fromthe occurrence of cracks, when exposed to a high temperature such as asolder reflow, and has a low dielectric constant.

According to the present invention 5, there is provided, as a morepreferable product, a sealing epoxy resin composition according to theabove, wherein, in the phenylene ether oligomer compound having an epoxygroup at each terminal represented by the formula (9), R2, R3, R4, R8and R9 in —X— are a methyl group, further at least one of R5, R6 and R7in —X— may be a methyl group, and Y—O— is an arrangement of the formula(6) or the formula (7) or a random arrangement of the formula (6) andthe formula (7).

According to the present invention 5, there is provided a sealing epoxyresin composition according to the above, wherein the content of thephenylene ether oligomer compound having an epoxy group at each terminalrepresented by the formula (9) is in the range of from 1 to 60% byweight based on the total amount of the epoxy resin, the curing agent,the inorganic filler and the oligomer compound itself.

According to the present invention 5, there is provided a sealing epoxyresin composition according the above, wherein the content of theinorganic filler is in the range of from 15 to 95% by weight based onthe total amount of the epoxy resin, the curing agent, the inorganicfiller and the oligomer compound.

Since the epoxy resin composition of the present invention 5 containsthe phenylene ether oligomer compound having an epoxy group at eachterminal, it has a low dielectric constant and excellent mechanicalstrength and has a low melt viscosity. When the melt viscosity of theabove resin composition is low, a resin flowability is good at asealing-molding time and no voids occur so that moldability isexcellent.

The bifunctional PEO-2Ep has a low melt viscosity and fine flowabilityand is excellent in compatibility with the epoxy resin. Further, it hasepoxy groups at both terminals so that the resin composition has highadhesive properties and its sealing layer is further excellent instrength under heat. As a result, when the sealing layer is exposed to ahigh temperature at soldering or the like, the occurrence of cracks canbe prevented. Further, since a polyphenylene ether is a material havinglow dielectric characteristics, there can be provided a sealing layerhaving low dielectric characteristics.

In the sealing epoxy resin composition of the present invention 5, thecontent of the bifunctional PEO-2Ep is preferably in the range of from 1to 60% by weight, more preferably 5 to 50% by weight, based on the totalamount of the epoxy resin, the bifunctional PEO-2Ep and the curingagent. When the above content is lower than 1% by weight, cracks are aptto occur in the sealing layer. When the above content is higher than 60%by weight, the melt viscosity increases at a sealing-molding so thatvoids occur and moldability is decreased.

Examples of the inorganic filler which is an ingredient of the sealingepoxy resin composition of the present invention include inorganicpowders such as silica and alumina. The preferable content of theinorganic filler varies depending upon a use.

For example, concerning a use as a sealing material for a pottingmolding, the content of the inorganic filler is preferably in the rangeof from 15 to 60% by weight, more preferably from 20 to 50% by weight,based on the total amount of the epoxy resin, the bifunctional PEO-2Ep,the curing agent and the inorganic filler. In this case of a use as asealing material for a potting molding, when the content of the aboveinorganic filler is less than 15% by weight, the strength of a sealinglayer is low. When the above content is more than 60% by weight,moldability decreases at a sealing-molding.

Further, concerning a use as a sealing material for a injection-molding,the content of the inorganic filler is preferably in the range of from60 to 95% by weight, more preferably from 70 to 90% by weight, based onthe total amount of the epoxy resin, the bifunctional PEO-2Ep, thecuring agent and the inorganic filler. In this case of a use as asealing material for a injection-molding, when the content of the aboveinorganic filler is less than 70% by weight, the moisture absorptioncoefficient of a sealing layer increases so that cracks are apt tooccur. When the above content is more than 95% by weight, the meltviscosity increases at a sealing-molding so that voids occur andmoldability decreases.

The above inorganic filler is preferably surface-treated with a couplingagent for improving conformability with the epoxy resin. Examples of thecoupling agent include silane coupling agents such asγ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane andN-phenyl-γ-aminopropyltrimethoxysilane.

The above sealing epoxy resin composition may contain a curingaccelerator, a releasing agent, a coloring agent, a flame retardant anda stress reducing agent, as required, in addition to the epoxy resin,the bifunctional PEO-2Ep, the curing agent and the inorganic filler.

Examples of the above curing accelerator include tertiary amines such as1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine andbenzyldimethylamine, imidazoles such as 2-methylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole and2-phenyl-4-methylimidazole, organic phosphines such as tributylphosphineand triphenylphosphine. Of these, triphenylphosphine improves theelectric characteristics of a sealing layer and thereforetriphenylphosphine is preferred.

Examples of the releasing agent include carnauba wax, stearic acid,montanoic acid and a carboxyl group-containing polyolefine. Examples ofthe coloring agent include carbon black. Examples of the above flameretardant include antimony trioxide. Examples of the stress reducingagent include silicone gel, silicone rubber and silicone oil.

According to the present invention 6, concerning a printed wiring boardmaterial, there are provided a thermosetting resin composition whichsatisfies severer requirements for lower dielectric characteristicswithout deteriorating conventional characteristic properties such asexcellent moldability and heat resistance and which also hasflexibility, a laminate using the same and a printed wiring board usingthe same.

The present invention 6 provides a resin composition for laminates,containing as an ingredient a phenylene ether oligomer cyanate compoundhaving a number average molecular weight of 700 to 3,000 and having acyanate group at each terminal, represented by the formula (10),N≡C—O

Z

_(c)

Y—O

_(a)X

O—Y

_(b)

Z

_(d)O—C≡N  (10)

wherein —X—, Y—O—, a and b are as defined in the formula (1) and Z, cand d are as defined in the formula (4).

The present invention 6 further provides a resin composition forlaminates, which contains as ingredients the phenylene ether oligomercyanate compound having a number average molecular weight of 700 to3,000 and having a cyanate group at each terminal, represented by theformula (10), a different cyanate ester resin and an epoxy resin.

Further, the present invention 6 provides a resin composition forlaminates according to the above, wherein, in the cyanate compound ofthe formula (10), R2, R3, R4, R8 and R9 in —X— are a methyl group,further at least one of R5, R6 and R7 in —X— may be a methyl group, Y—O—is an arrangement of the formula (6) or the formula (7) or a randomarrangement of the formula (6) and the formula (7).

The resin composition for laminates, provided by the present invention6, contains the phenylene ether oligomer cyanate compound having acyanate group at each terminal so that the resin composition has lowdielectric characteristics and excellent flexibility and has a low meltviscosity. When the above melt viscosity of the resin composition islow, the embeddability of a resin is fine at a laminate-molding time andno voids occur so that moldability is fine.

The phenylene ether oligomer cyanate compound of the formula (10) havinga cyanate group at each terminal (to be referred to as “bifunctionalPEO-2CN” hereinafter), provided by the present invention 6, will beexplained.

The above bifunctional PEO-2CN is obtained by reacting the bifunctionalPEO of the formula (1) with cyanogen halide such as cyanogen chloride orcyanogen bromide in the presence of a base in dehydrohalogenation.

Typical examples of the base include tertiary amines such astrimethylamine, triethylamine, tripropylamine, dimethylaniline andpyridine, sodium hydroxide, potassium hydroxide, sodium methoxide,sodium ethoxide, calcium hydroxide, sodium carbonate, potassiumcarbonate and sodium bicarbonate. The base shall not be limited tothese.

Typical examples of a solvent for the reaction includes toluene, xylene,chloroform, methylene chloride, carbon tetrachloride, chlorobenzene,nitrobenzene, nitromethane, acetone, methyl ethyl ketone,tetrahydrofuran and dioxane. The solvent shall not be limited to these.

When cyanogen chloride is used, the reaction temperature is preferablybetween −30° C. and +13° C. (boiling point). When cyanogen bromide isused, it is preferably between −30° C. and +65° C.

The number average molecular weight of the thus-obtained bifunctionalPEO-2CN is limited in the range of from 700 to 3,000. The abovebifunctional PEO-2CN has a low melt viscosity so that its flowability ishigh. It is excellent in compatibility with a different resin. Further,since it has cyanate groups at both terminals, the resin compositioncontaining it has good adhesive properties. As a result thereof, whenthe resin composition is exposed to a high temperature at soldering orthe like after moisture absorption, the occurrence of swellings can beprevented. Further, since a polyphenylene ether resin is a materialhaving low dielectric characteristics, there can be provided a laminatehaving low dielectric characteristics.

In the resin composition for laminates, provided by the presentinvention 6, the content of the bifunctional PEO-2CN is preferably inthe range of from 1 to 60% by weight, more preferably 5 to 50% byweight, based on the total amount of the bifunctional PEO-2CN, the epoxyresin, and the different cyanate resin. When the above content is lowerthan 1% by weight, sufficient flexibility is not obtained. When theabove content is higher than 60% by weight, the melt viscosity increasesso that voids occur at a laminate-molding, which decreases moldability.

Examples of the cyanate resin, which is an ingredient of the resincomposition of the present invention 6, include 1,3- or1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-,2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene,4,4′-dicyanatobiphenyl, bis(4-cyanatophenyl)methane,2,2-bis(4-cyanatophenyl)propane,2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether,bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone,tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate,4,4′-dicyanato-3,3′,5,5′-tetramethylbiphenyl,4,4′-dicyanato-2,2′,3,3′,5,5′-hexamethylbiphenyl, and cyanates obtainedby a reaction of novolak with cyanogen halide.

As an epoxy resin which is an ingredient of the resin composition of thepresent invention 6, there may be used those epoxy resins which havebeen disclosed in the present invention 3.

The resin composition for laminates, provided by the present invention6, may be used in combination with various resins according to a purposeand use. Specific examples of the resins include oxetane resins,acrylates, methacrylates esters; polyallyl compounds such as diallylbenzene and diallyl terephthalate; vinyl compounds such asN-vinyl-2-pyrolidone and divinyl benzene; polymerizabledouble-bond-containing monomers such as unsaturated polyester;polyfunctional maleimides; polyimides; rubbers such as polybutadiene,thermoplastic resins such as polyethylene, polystyrene and ABS; andengineering plastics such as PPE and polycarbonate. The above resinsshall not be limited to these resins.

Further, the resin composition may contain various additives such as aknown inorganic or organic filler, a dye, a pigment, a thickener, alubricant, an antifoamer, a coupling agent, a photosensitizer, anultraviolet absorber and a flame retardant, as required.

Although the composition of the present invention 6 undergoes curingitself under heat, a heat-curing catalyst can be incorporated in thecomposition for increasing the curing rate and improving workability andeconomic efficiency. There may be used a generally known heat-curingcatalyst as a heat-curing catalyst for the resin to be used incombination.

A copper-clad laminate using the resin composition for laminates,provided by the present invention 6, is particularly suitably used for aprinted wiring board which is required to have low dielectriccharacteristic. The copper-clad laminate of the present invention 6 isproduced by a generally known method. That is, it is a method in which abase material is impregnated with a resin varnish which is a solution ofa thermosetting resin composition in an organic solvent, the basematerial is heat-treated to obtain prepreg, and then the prepreg and acopper foil are laminated and molded under heat to obtain a copper-cladlaminate. However, the production method of the copper-clad laminateshall not be limited to this method.

As for the organic solvent used for the copper-clad laminate, the basematerial to be impregnated with the resin varnish, the heat-treatmentconditions, etc., in the present invention 6, there may be employedthose materials and conditions which have been disclosed in the presentinvention 4.

The present invention 7 provides a (meth)acrylate compound representedby the formula (11),

wherein R15 is a hydrogen atom or a methyl group, X—, Y—O—, a and b areas defined in the formula (1), Z′ is an organic group which have no OHgroup in a side chain, has one or more carbon atoms and may contain anoxygen atom, and c and d are as defined in the formula (4).

According to the present invention 7, further, there is provided a(meth)acrylate compound according to the above, wherein, in the(meth)acrylate compound of the formula (11), —X— is represented by theformula (5) and Y—O— has a arrangement structure of the formula (6) orthe formula (7) or a random arrangement structure of the formula (6) andthe formula (7).

According to the present invention 7, further, there is provided a(meth)acrylate compound according to the above, wherein Y—O— has astructure of the formula (7).

According to the present invention 7, further, there is provided acurable resin composition containing the above (meth)acrylate compound.

The (meth)acrylate compound of the present invention itself ispolymerized or it is copolymerized with a different unsaturatedcompound, whereby there is obtained a high molecular weight materialexcellent in heat resistance and dielectric characteristics. Further, aphotosensitive resin composition is obtained by combining the(meth)acrylate compound of the present invention with aphotopolymerization initiator. The thus-obtained photosensitive resincomposition is suitable for various uses for a resin for a resist, aresin for a buildup wiring board, a sealing resin for liquid-crystaldisplay panel, a color filter material for liquid-crystal display panel,a UV coating composition, various coating materials, an adhesive and thelike.

Preferably, in the formula (11), R2, R3, R4, R8 and R9 are an alkylgroup having 3 or less carbon atoms, R5, R6 and R7 are a hydrogen atomor an alkyl group having 3 or less carbon atoms, R10 and R11 are analkyl group having 3 or less carbon atoms, and R12 and R13 are anhydrogen atom or an alkyl group having 3 or less carbon atoms. Morepreferably, R2, R3, R4, R8 and R9 are a methyl group, R5, R6 and R7 area hydrogen atom or a methyl group, R10 and R11 are a methyl group, andR12 and R13 are an hydrogen atom or a methyl group. An organic group(which may contain an oxygen atom) having no OH group in a side chainand having one or more carbon atoms can be located at Z′. Examples of-(Z′-O—)— include —((CH₂)—O)—, —(CH₂CHRO)_(n)— and —(CH₂—Ar—O)—, whileit shall not be limited to these. The method of addition includes amethod in which the organic groups are directly added to an intermediaterepresented by the formula (1) and a method using a halide, while itshall not limited to these methods.

The method of producing the (meth)acrylate compound of the formula (11),provided by the present invention, is not specially limited. The(meth)acrylate compound of the formula (11) may be produced by anymethods. For example, the (meth)acrylate compound of the formula (11) isobtained by reacting a compound of the formula (12) with a (meth)acrylicacid or a (meth)acrylic acid derivative. Concretely, The (meth)acrylatecompound of the formula (11) is obtained by reacting a compound of theformula (12) with (meth) acrylic acid in the presence of anesterification catalyst such as p-toluenesulfonic acid, trifluoromethanesulfonic acid or sulfuric acid or its acid halide in the presence of,for example, an organic amine, sodium hydroxide or sodium carbonate, inthe presence of a solvent such as, preferably, toluene, xylene,cyclohexane, n-hexane, n-heptane or a mixture of these at a temperatureof preferably from 70° C. to 150° C.

The compound of the formula (12) is obtained by producing the compoundof the formula (1) by, for example, the method disclosed in JapanesePatent Application No. 2001-196569 and then introducing -(Z′-O)— into itas required.H

O-Z′

_(c)

O—Y

_(a)

O—XO

Y—O

_(b)

Z′-O

_(d)H  (12)

wherein —X—, Y—O—, a and b are as defined in the formula (1), Z′ is anorganic group which has no OH group in a side chain and has one or morecarbon atoms and which may contain an oxygen atom, and c and d are asdefined in the formula (4).

A case in which, for example, —(CH₂)_(m)O— or —(CH₂CHR₁₄O)_(n)— isintroduced as -(Z′-O)—, will be explained. —(CH₂)_(m)O— is introduced byreacting a compound of the formula (1) with a halogenated alcoholrepresented by the formula (13) in a proper solvent such as an alcohol,ether or a ketone in the presence of an alkaline catalyst such as KOH,K₂CO₃ or NaOEt, and —(CH₂CHR₁₄O)_(n)— is introduced by reacting acompound of the formula (1) with alkylene oxide represented by theformula (14) in a benzene solvent such as benzene, toluene or xylene inthe presence of an alkaline catalyst such as KOH, NaOEt or triethylamineaccording to, for example, a method disclosed in JP-B-52-4547,X—(CH₂)m—OH  (13)

wherein X is Cl or Br, and m is an integer of 2 or more,

wherein R16 is a hydrogen atom, a methyl group or an ethyl group.

Next, the curable resin composition of the present invention 7 will beexplained. The curable resin composition is characterized in that itcontains the above (meth)acrylate compound of the present invention. Thecurable resin composition of the present invention may contain a knownepoxy resin, an oxetane resin, a compound having an ethylenicunsaturated group, a photopolymerization initiator and/or a thermalpolymerization initiator, and a photosensitizer.

As the above epoxy resin, the oxetane resin and the compound having anethylenic unsaturated group, there may be used those resins andcompounds which have been disclosed in the present invention 3.

When the epoxy resin and/or the oxetane resin are used for the curableresin composition of the present invention, an epoxy resin curing agentand/or an oxetane resin curing agent may be used. As these curingagents, there may be used those curing agents which have been disclosedin the present invention 3.

As for the photopolymerization initiator, the photosensitizer and thethermal polymerization initiator, there may be used those materialswhich have been disclosed in the present invention 3.

Further, in the production of the curable resin composition of thepresent invention 7, there may be added known additives, as required,such as an inorganic filler, a color pigment, an antifoamer, a surfaceconditioner, a flame retardant, an ultraviolet absorber, an antioxidant,a polymerization inhibitor and a flow regulator, which are disclosed inthe production of the curable resin composition of the present invention3. The thus-obtained curable resin composition is suitable for varioususes for a solder resist composition, a buildup wiring board material,an insulating coating, an adhesive, a printing ink and a coatingmaterial.

EFFECT OF THE INVENTION

According to the present invention, there is provided a bifunctionalphenylene ether oligomer which is sufficiently soluble in a ketonesolvent and has high compatibility with a thermosetting resin and, forexample, from which a varnish for laminates is easily prepared and alaminate excellent in molding processability is produced. According tothe present invention, there is provided an oligomer of which theterminal phenolic hydroxyl groups are easily modified in a ketonesolvent. The oligomer of the present invention has as a basic structurea polyphenylene ether having low dielectric characteristics andstrength, which is one of engineer plastics, so that the oligomer is anelectric and electronic material having characteristic propertiessimilar to those of a PPE polymer.

According to the present invention, there is provided a thermosettingtype phenylene ether oligomer compound which is soluble in ageneral-purpose solvent and has high compatibility with a differentthermosetting resin. Therefore, for example, a varnish for laminates canbe easily prepared from the thermosetting type phenylene ether oligomercompound of the present invention and a laminate material excellent inmolding processability can be produced.

According to the present invention, there is provided an epoxy acrylatecompound having high glass transition temperature and having a lowdielectric constant and a low dielectric loss tangent. Due to thesecharacteristic properties, the epoxy acrylate compound of the presentinvention is remarkably useful as a high-function high molecular weightmaterial and is widely suitable, as a thermally and electricallyexcellent material, for uses for various coating agents, UV coatingcompositions, adhesives, resists and laminates.

According to the present invention, there is provided a resincomposition containing a phenylene ether oligomer epoxy compound, whichresin composition has high heat resistance and excellent electriccharacteristics such as low dielectric constant and low dielectric losstangent, is excellent in moldability and is well balanced. A laminate ora multilayer printed wiring board using the resin composition of thepresent invention is finely molded at a multilayer molding time and hashigh reliability. Further, the high speed processing of a high-frequencywave signal and a circuit design for low loss are possible.

According to the present invention, there is provided a sealing epoxyresin composition containing a bifunctional PEO-2Ep, which is capable ofgiving a sealing layer which is free from the occurrence of cracks, whenexposed to a high temperature at a solder reflow or the like, and haslow dielectric constant. Accordingly, there is provided a semiconductordevice having high reliability and having a chip circuit excellent intransmittal speed.

According to the present invention, there is provided a well-balancedresin composition containing a phenylene ether oligomer cyanatecompound, which resin composition has high heat resistance and lowdielectric characteristics and is excellent in moldability andflexibility. A laminate or a multilayer printed wiring board using theresin composition of the present invention is finely molded at amultilayer molding time and has high reliability. Further, thehigh-speed processing of a high-frequency wave signal and a circuitdesign for low loss are possible.

According to the present invention, there is provided an acrylatecompound which has a high glass transition temperature and has a lowdielectric constant and a low dielectric loss tangent and which istherefore remarkably useful as a high-function high molecular weightmaterial and is widely suitable, as a thermally and electricallyexcellent material, for uses for various coatings, UV coatingcompositions, adhesives, resists and buildup printed wiring boardmaterial.

EXAMPLES

The present invention will be explained concretely with reference toExamples and Comparative Examples, while the present invention shall notbe limited to these Examples. A number average molecular weight and aweight average molecular weight were measured according to the gelpermeation chromatography (GPC) method. Data processing was carried outaccording to the GPC curve and molecular weight calibration curve of asample. The molecular weight calibration curve was obtained by making anapproximation of a relation between the molecular weight of a standardpolystylene and the dissolution time thereof with the followingequation,Log M=A ₀ X ³ +A ₁ X ² +A ₂ X+A ₃ +A ₄ /X ²

wherein M: a molecular weight, X: an elution time−19 minutes, and A: acoefficient.

A hydroxyl group equivalent was determined from an absorption intensityat 3,600 cm⁻¹ in an IR analysis (solution cell method) using2,6-dimethylphenol as a standard reference material.

Example 1

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and a baffleplatewas charged with 2.7 g (0.012 mol) of CuBr₂, 70.7 g (0.55 mol) ofdi-n-butylamine and 600 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a mixture solution(bivalent phenol:monovalent phenol molar ratio=1:2) obtained bydissolving 55.7 g (0.21 mol) of a bivalent phenol(2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol) (a) and 50.4 g(0.41 mol) of 2,6-dimethylphenol in 600 g of methyl ethyl ketone wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 2 L/min of air. After the completion of the addition,stirring was carried out for 60 minutes while continuing the bubblingwith 2 L/min of air. A disodium dihydrogen ethylenediamine tetraacetateaqueous solution was added to the reaction mixture to terminate thereaction. Then, washing was carried out with 1N hydrochloric acidaqueous solution three times and then washing was carried out with purewater. The thus-obtained solution was concentrated by an evaporator, andthen a suction drying was carried out, to obtain 100.3 g of a reactionproduct. The reaction product had a number average molecular weight of650, a weight average molecular weight of 810 and a hydroxyl groupequivalent of 310 and it was soluble in methyl ethyl ketone. The aboveresin will be referred to as “(c)” hereinafter.

Example 2

The same longitudinally long reactor as that used in Example 1 wascharged with 1.3 g (0.013 mol) of CuCl, 79.5 g (0.62 mol) ofdi-n-butylamine and 600 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a mixture solution(bivalent phenol:monovalent phenol molar ratio=1:4) obtained bydissolving 41.8 g (0.16 mol) of a bivalent phenol(2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol) (a) and 75.6 g(0.62 mol) of 2,6-dimethylphenol in 600 g of methyl ethyl ketone wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 2 L/min of air. After the completion of the addition,stirring was carried out for 30 minutes while continuing the bubblingwith 2 L/min of air. Then, the termination of the reaction, washings,concentration and suction drying were carried out in the same manners asin Example 1, whereby 111.4 g of a reaction product was obtained. Thereaction product had a number average molecular weight of 1,110, aweight average molecular weight of 1,450 and a hydroxyl group equivalentof 580 and it was soluble in methyl ethyl ketone. The above resin willbe referred to as “(d)” hereinafter.

Example 3

The same longitudinally long reactor as that used in Example 1 wascharged with 1.1 g (0.011 mol) of CuCl, 66.3 g (0.51 mol) ofdi-n-butylamine and 500 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a mixture solution(bivalent phenol:monovalent phenol molar ratio=1:8) obtained bydissolving 20.9 g (0.077 mol) of a bivalent phenol(2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol) (a) and 75.6 g(0.62 mol) of 2,6-dimethylphenol in 600 g of methyl ethyl ketone wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 2 L/min of air. After the completion of the addition,stirring was carried out for 30 minutes while continuing the bubblingwith 2 L/min of air. Then, the termination of the reaction, washings,concentration and suction drying were carried out in the same manners asin Example 1, whereby 91.4 g of a reaction product was obtained. Thereaction product had a number average molecular weight of 1,700, aweight average molecular weight of 2,300 and a hydroxyl group equivalentof 820 and it was soluble in methyl ethyl ketone. The above resin willbe referred to as “(e)” hereinafter.

Example 4

The same longitudinally long reactor as that used in Example 1 was used.111.9 g of a reaction product was obtained in the same manner as inExample 2 except that the mixture solution used in Example 2 wasreplaced with a mixture solution (bivalent phenol:monovalent phenolmolar ratio=1:4) obtained by dissolving 41.8 g (0.15 mol) of2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol (a), 56.7 g (0.46mol) of 2,6-dimethylphenol and 21.1 g (0.16 mol) of 2,3,6,-trimethylphenol in 600 g of methyl ethyl ketone. The reaction producthad a number average molecular weight of 1,000, a weight averagemolecular weight of 1,350 and a hydroxyl group equivalent of 520 and itwas soluble in methyl ethyl ketone. The above resin will be referred toas “(f)” hereinafter.

Comparative Example 1

The same longitudinally long reactor as that used in Example 1 wascharged with 1.3 g (0.013 mol) of CuCl, 79.5 g (0.62 mol) ofdi-n-butylamine and 600 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a mixture solution(bivalent phenol:monovalent phenol molar ratio=1:4) obtained bydissolving 37.4 g (0.16 mol) of a bivalent phenol(3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol) (b) and 75.6 g (0.62mol) of 2,6-dimethylphenol in 520 g of methyl ethyl ketone was dropwiseadded to the reactor over 120 minutes while carrying out bubbling with 2L/min of air. After the completion of the addition, stirring was carriedout for 30 minutes while continuing the bubbling with 2 L/min of air, toobtain a large amount of precipitate in the reaction solution. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the reaction solution to terminate the reaction. A solid wasrecovered by filtration. Then, the obtained solid was washed withmethanol three times. An obtained solution was concentrated by anevaporator, and then a suction drying was carried out, to obtain 80.1 gof a reaction product. The reaction product had a number averagemolecular weight of 5,300, a weight average molecular weight of 9,000and a hydroxyl group equivalent of 3,800 and it was insoluble in methylethyl ketone. The above resin will be referred to as “(g)” hereinafter.

Comparative Example 2

The same longitudinally long reactor as that used in Example 1 wascharged with 1.3 g (0.013 mol) of CuCl, 48.7 g (0.62 mol) of pyridineand 600 g of methyl ethyl ketone. The components were stirred at areaction temperature of 40° C., and a mixture solution (bivalentphenol:monovalent phenol molar ratio=1:4) obtained by dissolving 41.8 g(0.16 mol) of a bivalent phenol(2,2′3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol) (a) and 75.6 g(0.62 mol) of 2,6-dimethylphenol in 520 g of methyl ethyl ketone wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 2 L/min of air. Then, stirring, the termination of thereaction, washings, concentration and suction drying were carried out inthe same manners as in Example 1, whereby 110.2 g of a reaction productwas obtained. The reaction product had a number average molecular weightof 1,100, a weight average molecular weight of 1,820 and a hydroxylgroup equivalent of 600. The above resin will be referred to as “(h)”hereinafter.

Table 1 shows the results of Examples and Comparative Examples.

According to Examples 1, 2 and 3, an increase in the molar ratio of thebivalent phenol increased the number average molecular weight and theweight average molecular weight and the bifunctional oligomers having adesired molecular weight distribution could be obtained by changing themolar ratio. According to the results of Example 2 and ComparativeExample 1, when the biphenol(3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol) having no substituentat 2-site (R4 in the formula (2)), as a bivalent phenol, was used as araw material, the oligomer having an average molecular weight of morethan 5,000 was generated. A bifunctional phenylene ether soluble inmethyl ethyl ketone was not effectively synthesized.

That is, the presence of substituent at 2-site (R4 in the formula (2))of the bivalent phenol is essential for effectively synthesizing abifunctional phenylene ether soluble in methyl ethyl ketone. Accordingto the results of Example 2 and Comparative Example 2, whendi-n-butylamine was used as an amine, there could be obtained anoligomer having a sharper molecular weight distribution than that of thecase where pyridine was used. According to the results of Example 2 andExample 4, when compared with the case where 2,6-dimethylphenol alonewas used as a monovalent phenol, the case where the mixture of2,6-dimethylphenol and 2,3,6-trimethylphenol was used as a monovalentphenol gave an oligomer having a lower molecular weight. The reason isthat the methyl group at the 3-site of 2,3,6-trimethylphenol preventedpolymerization and prevented the generation of a polymer.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 CEx. 1 CEx. 2 Resin c d e f g h Bivalenta a a a b a phenol molar ratio *¹ 2 4 8 4 4 4 Amine *² A A A A A B Mn650 1,110 1,700 1,000 5,300 1,100 Mw 810 1,450 2,300 1,350 9,000 1,820Mn/Mw 1.25 1.31 1.35 1.35 1.70 1.65 Hydroxyl 310 580 820 520 3,800 600group equivalent Solubility *³ ◯ ◯ ◯ ◯ X ◯ Ex. = Example, CEX =Comparative Example *¹ molar ratio: 2,6-dimethylphenol/bivalent phenol*² A: di-n-butylamine, B: pyridine *³ solubility in methyl ethyl ketone

Example 5

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas cooled down to −10° C. 200 ml of a methylene chloride solutioncontaining cyanogen chloride (0.129 mol) was placed in the reactor.Then, a solution obtained by dissolving 50.0 g (hydroxyl group 0.086mol) of the phenylene ether oligomer (bifunctional PEO) obtained inExample 2 and 13.1 g (0.129 mol) of triethylamine in 250 g of methylethyl ketone, was dropwise added from the dropping funnel over 60minutes so as to maintain the temperature of the reaction solution at10° C. or less. After the completion of the addition, stirring wascarried out for 60 minutes. Then, washing was carried out with 0.1Nhydrochloric acid aqueous solution three times, then washing was carriedout with pure water, and further a filtration was carried out, to removea generated salt and impurities. The methylene chloride and the methylethyl ketone were evaporated from the obtained solution, and a suctiondrying was carried out, to obtain 50.1 g of a cyanate compound.According to the IR analysis of the obtained cyanate compound, theabsorption peak (3,600 cm−1) of a phenolic hydroxyl group disappearedand the absorption peak (2,250 cm−1) derived from a cyanate groupappeared so that it was confirmed that all functional groups werechanged. 0.1 part by weight of tin octylate was added to 100 parts byweight of the thus-obtained cyanate compound. The melting, degassing andmolding thereof were carried out at 160° C., and curing was carried outat 230° C. for 3 hours, to obtain a cured product. The cured product hada glass transition temperature of 242° C. according to the measurementof dynamic viscoelasticity (DMA). Further, its dielectric constant at 1GHz was 2.73 and its dielectric loss tangent was 0.0061.

Example 6

111.9 g of a bifunctional PEO was obtained in the same manner as inExample 2. The bifunctional PEO had a number average molecular weight of1,000, a weight average molecular weight of 1,350 and a hydroxyl groupequivalent of 520.

50.8 g of a cyanate compound was obtained in the same manner as inExample 5 except that the methylene chloride solution containingcyanogen chloride (0.129 mol) used in the Example 5 was replaced with amethylene chloride solution containing cyanogen chloride (0.144 mol) andthat 13.1 g (0.129 mol) of triethylamine was replaced with 14.6 g (0.144mol) of triethylamine. According to the IR analysis of the obtainedcyanate compound, the absorption peak (3,600 cm−1) of a phenolichydroxyl group disappeared and the absorption peak (2,250 cm−1) derivedfrom a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

The thus-obtained cyanate compound was treated similarly to Example 5,to obtain a cured product. The cured product had a glass transitiontemperature of 251° C. according to the measurement of dynamicviscoelasticity (DMA). Further, its dielectric constant at 1 GHz was2.70 and its dielectric loss tangent was 0.0053.

Example 7

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas charged with 40.0 g (hydroxyl group 0.129 mol) of the bifunctionalPEO obtained in Example 1 and 360.0 g of epichlorohydrin. The mixturewas heated up to 100° C. Then, a solution obtained by dissolving 10.5 g(0.155 mol) of sodium ethoxide in 250 g of ethanol was dropwise addedfrom the dropping funnel over 60 minutes. After the completion of theaddition, stirring was carried out for 5 hours. Then, washing wascarried out with 0.1N hydrochloric acid aqueous solution three times,then washing was carried out with pure water, and further a filtrationwas carried out, to remove a generated salt and impurities. The excessepichlorohydrin was distilled off from the obtained solution, and asuction drying was carried out, to obtain 45.9 g of an epoxy compound.According to the IR analysis of the obtained epoxy compound, theabsorption peak (3,600 cm−1) of a phenolic hydroxyl group disappeared,and according to the NMR analysis, a peak derived from glycidyl etherappeared so that it was confirmed that all functional groups werechanged.

3 parts by weight of 1-benzyl-2-methylimidazole was added to 100 partsby weight of the thus-obtained epoxy compound. The melting, degassingand molding thereof were carried out at 150° C., and curing was carriedout at 180° C. for 10 hours, to obtain a cured product. The curedproduct had a glass transition temperature of 197° C. according to themeasurement of dynamic viscoelasticity (DMA). Further, its dielectricconstant at 1 GHz was 2.75 and its dielectric loss tangent was 0.0140.

Example 8

Example 3 was repeated till the washing with pure water except that 500g of methyl ethyl ketone in Example 3 was replaced with 500 g oftoluene, and that 600 g of methyl ethyl ketone in Example 3 was replacedwith 600 g of methanol.

The obtained solution was concentrated by an evaporator, to obtain a 70%bifunctional PEO toluene solution. Part of the above solution wasfurther concentrated and a suction drying was carried out, to obtain apowder. The bifunctional PEO had a number average molecular weight of1,620, a weight average molecular weight of 2,180 and a hydroxyl groupequivalent of 810.

Production Process of Allyl Compound

A solution obtained by dissolving 71.4 g (hydroxyl group 0.062 mol) ofthe above 70% bifunctional PEO toluene solution and 14.9 g (0.123 mol)of allyl bromide in 150 g of methylene chloride, and 120 ml of 1N sodiumhydroxide aqueous solution were placed in a reactor equipped with astirrer and a thermometer at room temperature. Further, 2.2 g (0.0062mol) of benzyltri-n-butylammonium bromide as a phase transfer catalystwas added to the reactor. The mixture was stirred for 5 hours. Then,washing was carried out with 0.1N hydrochloric acid aqueous solutionthree times, then washing was carried out with pure water, and further afiltration was carried out, to remove a generated salt and impurities.The methylene chloride was distilled off from the obtained solution, anda suction drying was carried out, to obtain 51.5 g of an allyl compound.According to the IR analysis of the obtained allyl compound, theabsorption peak (3,600 cm−1) of a phenolic hydroxyl group disappeared,and according to the NMR analysis, a peak derived from the allyl groupappeared so that it was confirmed that all functional groups werechanged.

The melting, degassing and molding of the allyl compound were carriedout at 150° C., and curing was carried out at 230° C. for 3 hours, toobtain a cured product. The cured product had a glass transitiontemperature of 216° C. according to the measurement of dynamicviscoelasticity (DMA). Further, its dielectric constant at 1 GHz was2.67 and its dielectric loss tangent was 0.0035.

Comparative Example 3

3 parts by weight of 1-benzyl-2-methylimidazole was added to 100 partsby weight of 3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-glycidyl etherwhich was a biphenyl type epoxy resin for a semiconductor-sealingmaterial. The mixture was molten, degassed and molded at 150° C. andthen cured at 180° C. for 10 hours, to obtain a cured product. The curedproduct had a glass transition temperature of 133° C. according to themeasurement of dynamic viscoelasticity (DMA). Further, its dielectricconstant at 1 GHz was 3.06 and its dielectric loss tangent was 0.030.

Comparative Example 4

3 parts by weight of 1-benzyl-2-methylimidazole was added to 100 partsby weight of dicyclopentadiene type epoxy for a semiconductor-sealingmaterial. The mixture was molten, degassed and molded at 150° C. andthen cured at 180° C. for 10 hours, to obtain a cured product. The curedproduct had a glass transition temperature of 182° C. according to themeasurement of dynamic viscoelasticity (DMA). Further, its dielectricconstant at 1 GHz was 2.90 and its dielectric loss tangent was 0.020.

The dielectric constant and the dielectric loss tangent were obtainedaccording to a cavity resonant oscillation method.

Table 2 shows the above results.

TABLE 2 Ex. 5 Ex. 6 Ex. 7 Ex. 8 CEx. 3 CEx. 4 dielectric 2.73 2.70 2.752.67 3.06 2.90 constant (1 GHz) dielectric 0.0061 0.0053 0.0140 0.00350.030 0.020 loss tangent (1 GHz) Tg(DMA)/° C. 242 251 197 216 133 182Ex. = Example, CEX = Comparative Example

Example 9

Synthesis of Bifunctional PEO

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and a baffleplatewas charged with 11.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 43.2 g (0.16 mol) of a bivalent phenol2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol and 58.6 g (0.48mol) of 2,6-dimethylphenol in 800 g of methyl ethyl ketone was dropwiseadded to the reactor over 120 minutes while carrying out bubbling with 2L/min of air. After the completion of the addition, stirring was carriedout for 60 minutes while continuing the bubbling with 2 L/min of air. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the reaction solution to terminate the reaction. Then, washingwas carried out with 1N hydrochloric acid aqueous solution three timesand then washing was carried out with pure water. The thus-obtainedsolution was concentrated by an evaporator, and a suction drying wascarried out, to obtain 96.7 g of a bifunctional PEO. The oligomer had anumber average molecular weight of 810, a weight average molecularweight of 1,105 and a hydroxyl group equivalent of 475.

Synthesis of Epoxy Compound

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas charged with 50 g (hydroxyl group 0.11 mol) of the above oligomerand 292 g of epichlorohydrin. The mixture was heated up to 100° C. Then,a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in30 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with 0.1N hydrochloric acidaqueous solution three times, then washing was carried out with purewater, and further a filtration was carried out, to remove a generatedsalt and impurities. The excess epichlorohydrin was distilled off fromthe obtained solution, and a suction drying was carried out, to obtain53.2 g of an epoxy compound. According to the IR analysis of theobtained epoxy compound, the absorption peak (3,600 cm−1) of a phenolichydroxyl group disappeared, and according to the NMR analysis, a peakderived from glycidyl ether appeared so that it was confirmed that allfunctional groups were changed. The resin had a number average molecularweight of 965, a weight average molecular weight of 1,213 and an epoxyequivalent of 543.

Synthesis of Epoxy Acrylate Compound

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 25 g of the above epoxy compound, 3.3 g of an acrylic acid,20 g of carbitol acetate, 0.13 g of triphenylphosphine and 13 mg ofhydroquinone methyl ether. The mixture was heated up to 120° C., and itwas allowed to react with stirring. During the reaction, an acid valuewas measured, and the reaction was continued until the acid value became2 mg KOH/g. The stirring time at 120° C. was 5 hours. The reactionsolution was diluted with 40 g of methyl ethyl ketone. The dilutedreaction solution was dropwise added to methanol to obtain a precipitateagain. A solid was recovered by a filtration, and then a suction dryingwas carried out to obtain 25.2 g of an epoxy acrylate compound. Theepoxy acrylate compound had a number average molecular weight of 1,375and a weight average molecular weight of 1,656.

Example 10

10 g of the epoxy acrylate compound obtained in Example 9 was molten,degassed and molded at 150° C. and then cured at 200° C. for 6 hours toobtain a cured product.

Example 11

6 g of the epoxy acrylate compound obtained in Example 9 was dissolvedin 4 g of carbitol acetate, and 0.6 g of Darocur 1173 (supplied by CibaSpecialty Chemicals, photopolymerization initiator) was added to thesolution to obtain a resin composition. The resin composition wasapplied to a copper-clad laminate surface with a screen printingmachine, and then dried with an air dryer at 80° C. for 30 minutes. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in methyl ethyl ketone, to obtain adevelopment pattern of the resin-cured product. A pencil mar strength(JIS K5400) of the resin-cured product was HB.

Example 12

Synthesis of Acid-Modified Epoxy Acrylate Compound

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 10 g of the epoxy acrylate compound obtained in Example 9,7 g of carbitol acetate and 2.5 g of tetrahydrophthalic acid anhydride.The mixture was heated up to 80° C., and it was allowed to react withstirring. After 8 hours, according to IR measurement, a peak derivedfrom the acid anhydride disappeared, and therefore the reaction wasterminated to obtain an acid-modified epoxy acrylate compound. The acidvalue of the acid-modified epoxy acrylate compound was 81 mg KOH/g. Theacid-modified epoxy acrylate compound had a number average molecularweight of 1,769 and a weight average molecular weight of 2,111.

Example 13

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound obtained in Example 12 to obtain a resincomposition. The resin composition was applied to a copper-clad laminatesurface with a screen printing machine, and then dried with an air dryerat 80° C. for 30 minutes. A pattern film was placed on the coating, andthe coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of the resin-cured product. A pencil mar strength(JIS K5400) of the resin-cured product was HB.

Comparative Example 5

38 g of tetramethylbisphenoldiglycidyl ether (YX4000: supplied by JapanEpoxy Resins Co., Ltd: epoxy equivalent 190) and 14.4 g of acrylic acidwere dissolved at 60° C. Then, 0.19 g of triphenylphosphine and 19 mg ofhydroquinone methyl ether were added to the mixture. The resultantmixture was heated up to 100° C., and the mixture was stirred for 10hours. During the reaction, an acid value was measured. After the acidvalue became 2 mg KOH/g, the mixture was cooled down to 60° C. to obtaina resin. The resin was a viscous liquid at 60° C.

Comparative Example 6

10 g of the resin obtained in Comparative Example 5 was molten, degassedand molded at 120° C. and then cured at 200° C. for 6 hours to obtain acured product.

Comparative Example 7

10 g of bisphenol A type epoxy acrylate (SP1509, supplied by SHOWAHIGHPOLYMER CO., LTD) was degassed and molded at 120° C. and then curedat 200° C. for 6 hours to obtain a cured product.

Comparative Example 8

10 g of novolak type epoxy acrylate (SP4010, supplied by SHOWAHIGHPOLYMER CO., LTD) was degassed and molded at 120° C. and then curedat 200° C. for 6 hours to obtain a cured product.

The cured products obtained in Example 10 and comparative Example 6, 7and 8 were evaluated for properties by the following methods.

Glass transition temperature (Tg): Obtained by dynamic viscoelasticitymeasurement (DMA). Measurements were carried out at an oscillationfrequency of 10 Hz.

Dielectric constant and dielectric loss tangent: Obtained according to acavity resonant oscillation method.

Table 3 shows the evaluation results of the above properties.

TABLE 3 Ex. 10 CEx. 6 CEx. 7 CEx. 8 Tg (° C.) 198 165 140 142 dielectric2.74 3.12 3.31 3.10 constant (1 GHz) dielectric 0.018 0.036 0.052 0.032loss tangent (1 GHz) Ex. = Example, CEX = Comparative Example

Example 14

Production Process of Bifunctional PEO-2Ep

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas charged with 40.0 g (hydroxyl group 0.077 mol) of the bifunctionalPEO obtained in Example 4 and 213.5 g of epichlorohydrin. The mixturewas heated up to 100° C. Then, a solution obtained by dissolving 6.3 g(0.092 mol) of sodium ethoxide in 22.0 g of ethanol was dropwise addedfrom the dropping funnel over 60 minutes. After the completion of theaddition, further, stirring was carried out for 5 hours. Then, washingwas carried out with 0.1N hydrochloric acid aqueous solution threetimes, then washing was carried out with pure water, and further afiltration was carried out, to remove a generated salt and impurities.The excess epichlorohydrin was distilled off from the obtained solution,and a suction drying was carried out, to obtain 43.1 g of a bifunctionalPEO-2Ep (number average molecular weight: 1,150). According to the IRanalysis of the obtained bifunctional PEO-2Ep [A], the absorption peak(3,600 cm−1) of a phenolic hydroxyl group disappeared, and according tothe NMR analysis, a peak derived from glycidyl ether appeared so that itwas confirmed that all functional groups were changed.

70 parts by weight of the above bifunctional PEO-2Ep, 20 parts by weightof tetrabromobisphenol A epoxy (supplied by Dainippon Ink And Chemicals,Incorporated, trade name: EPICLON-153), 10 parts by weight of4,4′-diaminodiphenylmethane and 0.07 part by weight of 2-methylimidazolewere dissolved in methyl ethyl ketone, to prepare a varnish having aresin content of 60% by weight. A glass cloth (NE glass product: tradename WEX983, supplied by Nitto Boseki Co., Ltd.) was impregnated withthe above varnish, and then it was treated with a hot-air dryer, toobtain B-stage prepreg. Eight sheets of the prepreg and a copper foil(thickness: 18 μm, supplied by Mitsui Mining & smelting Co., Ltd., tradename: 3EC-3) were stacked and these materials were hot-pressed at 200°C. in vacuum for 2 hours to obtain a 0.8 mm-thick copper-clad laminate.Table 5 shows the physical properties of the copper-clad laminate.

Example 15 and Comparative Examples 9 to 11

Copper-clad laminates were obtained in the same manner as in Example 14except that thermosetting resins were mixed in amount ratios shown inTable 4. As an exception, in Comparative Example 10, toluene was used asa solvent, since an ingredient was insoluble in methyl ethyl ketone.

TABLE 4 Ex. 14 Ex. 15 CEx. 9 CEx. 10 CEx. 11 Bifunctional 70 50 — — —PEO-2Ep General-purpose PPE — — — 30 — polymer Bisphenol A type — 30 —30 30 cyanate prepolymer 4,4′dimethyl 10 — 18 — — diphenylmethaneTetrabromobisphenol 20 20 20 20 20 A epoxy Bisphenol A epoxy — — 10 20 —Phenol novolak type — — 52 — 50 epoxy iron — 0.04 — 0.04 0.04acetylacetonate 2-methylimidazole 0.07 — 0.07 — — Ex. = Example, CEx. =Comparative Example

General-purpose PPE polymer: supplied by Mitsubishi Gas Chemical Co.,Inc., number average molecular weight: 24,000.

Bisphenol A type cyanate prepolymer: prepolymer of2,2-bis(4-cyanatophenyl)propane.

Tetrabromobisphenol A epoxy: EPICLON-153, supplied by Dainippon Ink AndChemicals, Incorporated.

Bisphenol A epoxy: DER-331L, supplied by Dow Chemical Japan Ltd.

Phenol novolak type epoxy: EPPN-201, supplied by Nippon Kayaku Co., Ltd.

TABLE 5 Ex. 14 Ex. 15 CEx. 9 CEx. 10 CEx. 11 Grass transition 191° C.217° C. 156° C. 202° C. 190° C. temperature (DMA method) Dielectric 3.43.5 4.2 3.5 4.0 constant(1 GHz) Dielectric loss 0.0078 0.0018 0.0210.0046 0.014 tangent (1 GHz) Copper-foil peeling 1.1 1.2 1.4 1.2 0.9strength (kN/m) Moldability ◯ ◯ ◯ X ◯ Heat resistance against solderingafter moisture absorption (number of swelling/number of testedspecimens) 1 hour treatment 0/3 0/3 0/3 2/3 0/3 2 hours treatment 0/30/3 0/3 3/3 0/3 3 hours treatment 0/3 0/3 2/3 3/3 1/3 Ex. = Example,CEx. = Comparative Example

In Examples and Comparative Examples, measurements were carried out bythe following devices and methods.

-   -   Grass transition temperature (Tg): Obtained by a loss tangent        (tan δ) peak of a dynamic viscoelasticity measurement.    -   Dielectric constant and dielectric loss tangent: Measured        according to a cavity resonant oscillation method.    -   Copper foil peeling strength: Peeling strength of a copper foil        having a width of 10 mm in a 90-degree direction was measured        according to JIS C6481.    -   Heat resistance against soldering after moisture absorption: A        sample was prepared by removing the entire copper foil, the        sample was treated for absorption under PCT conditions at        121° C. at 0.2 MPa for 1 to 3 hours and then the sample was        immersed in a solder bath at 260° C. for 30 seconds. The sample        was visually observed for the occurrence of a delamination        (swelling).    -   Moldability: Determined depending upon whether or not an        internal layer pattern of a 70 μm-thick copper foil could be        embedded without voids.

Referential Example 1 Production Process of Bifunctional PEO-2Ep (1)

(Production Process of Bifunctional PEO)

A phenylene ether oligomer solution was obtained in the same manner asin Example 3 except that 500 g of methyl ethyl ketone was replaced with500 g of toluene and that 600 g of methyl ethyl ketone was replaced with600 g of methanol. The obtained solution was concentrated by anevaporator to obtain a 70% bifunctional PEO toluene solution. Part ofthe solution was further concentrated, and a suction drying was carriedout to obtain a powder. The powder had a number average molecular weightof 1,620, measured by the GPC method, and a hydroxyl group equivalent of810.

(Production Process of Bifunctional PEO-2Ep)

41.5 g of a bifunctional PEO-2Ep (number average molecular weight:1,780, to be referred to as “bifunctional PEO-2Ep [B]” hereinafter) wasobtained in the same manner as in Example 14 except that 57.1 g(hydroxyl group: 0.049 mol) of the above-obtained bifunctional PEOtoluene solution, 228.5 g of epichlorohydrin, 14.2 g of ethanol and 4.0g (0.059 mol) of sodium ethoxide were used. According to the IR analysisof the obtained bifunctional PEO-2Ep [B], a peak derived from glycidylether appeared so that it was confirmed that all functional groups werechanged.

Referential Example 2 Production Process of Bifunctional PEO-2Ep (2)

(Production Process of Bifunctional PEO)

A 70% bifunctional PEO toluene solution was obtained in the same manneras in Referential Example 1 except that there was used a mixturesolution (bivalent phenol:monovalent phenol molar ratio=1:15) obtainedby dissolving 11.9 g (0.044 mol) of2,2′,3,3′,5,5′-hexamethyl-(1,1′-biphenyl)-4,4′-diol and 79.9 g (0.66mol) of 2,6-dimethylphenol in 600 g of methanol. Part of the solutionwas further concentrated, and a suction drying was carried out to obtaina powder. The powder had a number average molecular weight of 3,340 anda hydroxyl group equivalent of 1,660. The number average molecularweight was measured in the same manner as in Referential Example 1.

(Process for the Production of Bifunctional PEO-2Ep)

49.8 g of a bifunctional PEO-2Ep (number average molecular weight:3,500, to be referred to as “bifunctional PPE-2Ep [C]” hereinafter) wasobtained in the same manner as in Referential Example 1 except that 71.4g (hydroxyl group: 0.024 mol) of the above-obtained bifunctional PEOtoluene solution, 155.7 g of epichlorohydrin, 6.9 g of ethanol and 2.0 g(0.029 mol) of sodium ethoxide were used. According to the same methodas that in Referential Example 1, it was confirmed that all functionalgroups were changed.

Referential Example 3 Production Process of an Epoxy-ModifiedPolyphenylene Ether

47.7 g of an epoxy-modified polyphenylene ether (to be referred to as“epoxy-modified PPE” hereinafter, number average molecular weight:16,000) was obtained in the same manner as in Referential Example 1except that 50 g of a commercially available polyphenylene ether resin(supplied by Mitsubishi Gas Chemical Co., Inc., number average molecularweight: 16,000, hydroxyl group: 0.003 mol), 200 g of toluene, 2.9 g ofepichlorohydrin, 2.2 g of ethanol and 0.6 g (0.009 mol) of sodiumethoxide were used. According to the same method as that in ReferentialExample 1, it was confirmed that 95% of functional groups were changed.

Example 16

There were used 32.40 parts by weight (7.02% by weight) of YX400H(supplied by Japan Epoxy Resins Co., Ltd, epoxy equivalent 195) as abiphenyl type epoxy resin, 10.80 parts by weight (2.34% by weight) of195XL (supplied by Sumitomo Chemical Co., Ltd., epoxy equivalent 195) asa cresol novolak type epoxy resin, 3.78 parts by weight (0.82% byweight) of EBS400T (supplied by Sumitomo Chemical Co., Ltd., epoxyequivalent 400) as a flame-retardant bisphenol type epoxy resin, 11.5parts by weight (2.49% by weight) of bifunctional PEO-2Ep [B], 15.93parts by weight (3.45% by weight) of KAYAHARD NHN (supplied by NipponKayaku Co., Ltd., hydroxyl group equivalent 140) as a naphthalene typephenol resin composition, 15.93 parts by weight (3.45% by weight) ofMILEX 225-3L (supplied by Mitsui Chemicals, Inc., hydroxyl equivalent173) as a P-xylylene-phenol copolymer, a powder obtained by treating360.50 parts by weight (78.08% by weight) of a fused silica powder with2.13 parts by weight (0.46% by weight) ofγ-glycidoxypropyltrimethoxysilane, 0.95 part by weight (0.21% by weight)of triphenylphosphine, 1.36 parts by weight (0.30% by weight) of naturalcarnauba, 0.99 parts by weight (0.21% by weight) of carbon black and5.40 parts by weight (1.17% by weight) of antimony trioxide. First, thebifunctional PEO-2Ep [B] and the epoxy resins were dissolved in thetoluene, to obtain a homogenous toluene solution having a concentrationof 30% by weight. The toluene was removed from the above toluenesolution, to obtain a mixture of the epoxy resins and the bifunctionalPEO-2Ep. The above materials were added to the mixture and the resultantmixture was kneaded with a heating roller at 85° C. for approximately 5minutes. Then, the kneaded mixture was pulverized so as to have adiameter of approximately 5 mm, whereby a sealing epoxy resincomposition was obtained.

Examples 17 to 19 and Comparative Examples 12 to 14

Sealing epoxy resin compositions were obtained in the same manner as inExample 16 except that materials were mixed in amount ratios shown inTable 6. The obtained sealing epoxy resin compositions of Examples 16 to19 and Comparative Examples 12 to 14 were subjected to a test of heatresistance against soldering, and these resin compositions wereevaluated for dielectric constant. Further, the resin compositions weremeasured for melt viscosity, cured products thereof were measured forbending strength, and the resin compositions were measured formoldability when used for sealing.

The above moldability test and the test of heat resistance againstsoldering were carried out under the following conditions. Asemiconductor chip having 7.6 mm×7.6 mm×0.4 mm (thickness) was mountedon an alloy lead frame having a die pad size of 8.2 mm×8.2 mm with asilver paste, and molding was carried out by using a 60-pin flat packagemolding die having an outside dimension of 19 mm×15 mm×1.8 mm(thickness) to prepare a test specimen. The obtained test specimen waschecked for existence or nonexistence of voids in a sealing layer withan ultrasonic exploratory device. When no voids existed, moldability wasgood (expressed by ◯). When voids existed, moldability was poor(expressed by X). Further, five test specimens were prepared in theabove manner. Each of the test specimens was allowed to absorb moistureat 85° C. at 85% RH for 72 hours, then it was immersed in a solderhaving a temperature of 260° C. for 10 seconds. The procedures ofabsorption and immersion were carried out two times. After thesoldering, the sealing layer was checked for existence or nonexistenceof cracks with an ultrasonic exploratory device and the sealing layerhaving cracks was considered to be defective.

The above dielectric constant was measured on the basis of themeasurement method of a molded article according to JIS-K-6911.

The bending strength of a cured product was measured as follows. Asealing epoxy resin composition was cured to prepare a test specimenhaving a size of 10 mm×4 mm×100 mm, the test specimen was measured forthree-point bending strength at room temperature and at 240° C. underconditions of distance between supports=64 mm and a crosshead speed=2mm/min.

The above melt viscosity of the resin composition was measured at 175°C. with an elevated type flow tester.

Table 7 shows the above results. It was confirmed that moldability wasgood, no voids occurred, dielectric constant was low, bending strengthwas high and the melt viscosity was low, when the bifunctional PEO-2Epshaving a number average molecular weight of 700 to 3,000 were used.

TABLE 6 (Unit: % by weight) Ex. Ex. EX. Ex. CEx. CEx. CEx. 16 17 18 1912 13 14 Epoxy YX4000H 7.02 6.06 9.36 7.02 7.02 7.02 8.87 resin 195XL2.34 2.34 2.34 2.34 2.98 EBS400T 0.82 0.82 0.82 0.82 0.82 0.82 0.82Bifunctional 2.49 PEO-2Ep[A] Bifunctional 2.49 5.79 2.49 PEO-2Ep[B]Bifunctional 2.49 PEO-2Ep[C] Epoxy-modified PPE 2.49 KAYAHARD NHN 3.453.45 3.45 3.45 3.45 3.45 3.45 MILEX 225-3L 3.45 3.45 3.45 3.45 3.45 3.453.45 Fused silica 78.08 78.08 78.08 78.08 78.08 78.08 78.08 powderCoupling agent 0.46 0.46 0.46 0.46 0.46 0.46 0.46 Triphenyl 0.21 0.210.21 0.21 0.21 0.21 0.21 phosphine Natural 0.30 0.30 0.30 0.30 0.30 0.300.30 carnauba Carbon black 0.21 0.21 0.21 0.21 0.21 0.21 0.21 antimony1.17 1.17 1.17 1.17 1.17 1.17 1.17 trioxide Ex. = Example, CEx. =Comparative Example Note: As a bifunctional PEO-2Ep [A], thebifunctional PEO-2Ep [A] obtained in Example 14 was used.

TABLE 7 Ex. Ex. EX. Ex. CEx. CEx. CEx. 16 17 18 19 12 13 14 Number ofthe 0/5 0/5 0/5 0/5 2/5 5/5 5/5 occurrence of cracks after solderingNumber of defectives/ Number of specimens tested dielectric 4.6 4 .1 4.64.6 4.6 4.4 5.1 constant Moldability ◯ ◯ ◯ ◯ ◯ X ◯ Bending Room 156 160157 156 147 148 144 strength temperature (MPa) 240° C. 12.7 13.7 12.711.7 7.8 8.8 5.9 Melt viscosity 30 34 22 25 37 94 20 (Pa · s) Ex. =Example, CEx. = Comparative Example

Example 20

The bifunctional PEO produced in Example 2 was used. The bifunctionalPEO was treated in the same manner as in Example to obtain 50.1 g of acyanate compound (bifunctional PEO-2CN). According to the IR analysis ofthe obtained cyanate compound, the absorption peak (3,600 cm−1) of aphenolic hydroxyl group disappeared and an absorption peak (2,250 cm−1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

30 parts by weight of the above bifunctional PEO-2CN, 30 parts by weightof bisphenol A type cyanate prepolymer, 20 parts by weight oftetrabromobisphenol A epoxy (supplied by Dainippon Ink And Chemicals,Incorporated, trade name: EPICLON-153), 20 parts by weight of bisphenolA epoxy (supplied by Dow Chemical Japan Ltd., trade name: DER-331L) and0.04 part of iron acetylacetonate were dissolved in methyl ethyl ketone,to prepare a varnish having a resin content of 60% by weight.

A glass cloth (NE glass product: trade name WEX983, supplied by NittoBoseki Co., Ltd.) was impregnated with the above varnish, and then itwas treated with a hot-air dryer, to obtain B-stage prepreg. Eightsheets of the prepreg and a copper foil (thickness: 18 μm, supplied byMitsui Mining & smelting Co., Ltd., trade name: 3EC-3) were laminatedand these materials were hot-pressed at 200° C. in vacuum for 2 hours toobtain a 0.8 mm-thick copper-clad laminate. Table 9 shows the physicalproperties of the copper-clad laminate.

Comparative Example 15, 16

Copper-clad laminates were obtained in the same manner as in Example 20except that thermosetting resins were mixed in amount ratios shown nTable 8. In Comparative Example 15, toluene was used as a solvent, sincean ingredient was insoluble in methyl ethyl ketone.

TABLE 8 Ex. 20 CEx. 15 CEx. 16 Bifunctional 30 — — PEO-2EpGeneral-purpose PPE — 30 — polymer Bisphenol A type 30 30 30 cyanateprepolymer 4,4′dimethyl — — — diphenylmethane Tetrabromobisphenol 20 2020 A epoxy Bisphenol A epoxy 20 20 10 Phenol novolak type — — 40 epoxyiron 0.04 0.04 0.04 acetylacetonate Ex. = Example, CEx. = ComparativeExample

TABLE 9 Ex. 20 CEx. 15 CEx. 16 Grass transition 210° C. 202° C. 190° C.temperature (DMA method) Dielectric 3.5 3.5 4.0 constant (1 GHz)Dielectric loss 0.0048 0.0046 0.014 tangent (1 GHz) Copper-foil peeling1.2 1.2 0.9 strength (kN/m) Moldability ◯ X ◯ Heat resistance againstsoldering after moisture absorption (number of swelling/number of testedspecimens) 1 hour treatment 0/3 2/3 0/3 2 hours treatment 0/3 3/3 0/3 3hours treatment 0/3 3/3 1/3 Bending strength 485 368 498 (MPa) bendelastic constant 17800 17200 19200 (MPa) Bending flexibility 2.9 2.4 2.8coefficient(%) Ex. = Example, CEx. = Comparative Example

-   -   Mechanical Properties

Head speed: 1.0 mm/min, distance between supports: 20 mm, measured atroom temperature.

Example 21

[Synthesis of Bifunctional PEO]

A longitudinally long reactor having a volume of 5 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and a baffleplatewas charged with 13.3 g (0.030 mol) of CuCl, 176.8 g (1.34 mol) ofdi-n-butylamine and 1,000 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 108.0 g (0.40 mol) of a bivalent phenol,2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diol, and 146.5 g (1.20mol) of 2,6-dimethylphenol in 2,000 g of methyl ethyl ketone wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 5 L/min of air. After the completion of the addition,stirring was carried out for 60 minutes while continuing the bubblingwith 5 L/min of air. A disodium dihydrogen ethylenediamine tetraacetateaqueous solution was added to the reaction mixture to terminate thereaction. Then, washing was carried out with 1N hydrochloric acidaqueous solution three times and then washing was carried out with purewater. The thus-obtained solution was concentrated by an evaporator andthen a suction drying was carried out, to obtain 241.8 g of abifunctional PEO resin. The resin had a number average molecular weightof 810, a weight average molecular weight of 1,105 and a hydroxyl groupequivalent of 475.

(Introduction of Z-Site)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 50 g (hydroxyl group 0.11 mol) of the above bifunctionalPEO resin, 14.5 g of potassium carbonate and 400 ml of acetone and themixture was refluxed under nitrogen for 3 hours. Then, 21.0 g of6-bromo-1-hexanol was dropwise added to the mixture over 1 hour. Afterthe completion of the addition, the mixture was further refluxed for 30hours. After neutralization with 1N hydrochloric acid aqueous solution,a large amount of pure water was added to the mixture to obtain aprecipitate, and toluene was added to perform extraction. The obtainedsolution was concentrated by evaporator, and the concentrated solutionwas dropwise added to methanol to obtain a precipitate again. A solidwas recovered by a filtration. Then, a suction drying was carried out toobtain 54.7 g of a bifunctional PEO resin having z-sites introducedthereto. The resin had a number average particle diameter of 1,024 aweight average particle diameter of 1,385 and a hydroxyl groupequivalent of 579.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above bifunctional PEO resin having z-sites,4.5 g of an acrylic acid, 30 g of toluene, 0.12 g of p-toluenesulfonicacid and 0.03 of hydroquinone. The mixture was allowed to react underheat with refluxing. A generation water was quantified and collectedwith a water quantitative receiver. At the time when 0.8 g of thegeneration water was collected, the reaction mixture was cooled. Thereaction temperature was 110 to 120° C. The reaction mixture wasneutralized with 20% NaOH aqueous solution and then washed with 20% NaClaqueous solution three times. The solvent was evaporated under a reducedpressure, to obtain 29.5 g of an acrylate resin. The acrylate resin hada number average molecular weight of 1,188 and a weight averagemolecular weight of 1,562.

Example 22

Introduction of Z-Site

An airtight reactor was charged with 50 g of the above bifunctional PEOresin obtained in Example 21, and 20 g of toluene and 1 g of potassiumhydroxide as a catalyst were added to the reactor. The inside atmosphereof the reactor was substituted with nitrogen. Then, the mixture washeated with stirring, and at the time when the inside temperaturereached 70° C. 5.1 g of ethylene oxide was press-injected to themixture. The mixture was further heated up to 100° C. and an additionreaction was carried out at 100° C. for 4 hours. Further, the reactionmixture was aged for 1 hour. The reaction product was neutralized with1N hydrochloric acid aqueous solution and the washed with pure water.The solvent was evaporated under a reduced pressure, to obtain 49.2 g ofa resin. The bifunctional PEO resin having Z-sites introduced theretohad a number average particle diameter of 901, a weight average particlediameter of 1,213 and a hydroxyl group equivalent of 524.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above bifunctional PEO resin having z-sites,4.9 g of an acrylic acid, 30 g of toluene, 0.13 g of p-toluenesulfonicacid and 0.03 of hydroquinone. The mixture was allowed to react underheat with refluxing. A generation water was quantified and collectedwith a water quantitative receiver. At the time when 0.9 g of thegeneration water was collected, the reaction mixture was cooled. Thereaction temperature was 110 to 120° C. The reaction mixture wasneutralized with 20% NaOH aqueous solution, and then washed with 20%NaCl aqueous solution three times. The solvent was evaporated under areduced pressure, to obtain 29.7 g of an acrylate resin. The acrylateresin had a number average molecular weight of 1,042 and a weightaverage molecular weight of 1,377.

Example 23

Introduction of Z-Sites

50.5 g of a bifunctional PEO resin having z-sites introduced wasobtained in the same manner as in Example 22 except that 20 g of toluenewas replaced with 25 g of toluene and 5.1 g of the ethylene oxide wasreplaced with 6.7 g of propylene oxide. The resin had a number averageparticle diameter of 941, a weight average particle diameter of 1,255and a hydroxyl group equivalent of 541.

(Synthesis of an Acrylate Compound)

The above resin was treated in the same manner as in Example 22, toobtain 29.3 g of an acrylate resin. The acrylate resin had a numberaverage molecular weight of 1,084 and a weight average molecular weightof 1,422.

Example 24

10 g of the acrylate resin obtained in Example 21 was molten, degassedand molded at 150° C. and then cured at 200° C. for 6 hours, to obtain acured product.

Example 25

10 g of the acrylate resin obtained in Example 22 was molten, degassedand molded at 150° C. and then cured at 200° C. for 6 hours, to obtain acured product.

Example 26

10 g of the acrylate resin obtained in Example 23 was molten, degassedand molded at 150° C. and then cured at 200° C. for 6 hours, to obtain acured product.

Example 27

6 g of the acrylate compound obtained in Example 21 was dissolved in 4 gof carbitol acetate, and 0.6 g of Darocur 1173 (supplied by CibaSpecialty Chemicals, photopolymerization initiator) was added to thesolution to obtain a resin composition. The resin composition wasapplied to a copper-clad laminate surface by a screen printing machine,and then dried with an air dryer at 80° C. for 60 minutes. A patternfilm was placed on the coating, and the coating was exposed at 1,500 mJwith a UV irradiation device (supplied by EYE GRAPHICS Co. Ltd.: UB0151,light source: metal halide lamp). After the exposure, development wascarried out with methyl ethyl ketone. In this case, only non-exposedportions were dissolved in methyl ethyl ketone, to obtain a developmentpattern of the resin-cured product. A pencil mar strength (JIS K5400) ofthe resin-cured product was B.

Example 28

6 g of the acrylate resin obtained in Example 22 was treated in the samemanner as in Example 27, to obtain a development pattern of aresin-cured product in which only non-exposed portions were dissolved inmethyl ethyl ketone. A pencil mar strength (JIS K5400) of theresin-cured product was B.

Example 29

6 g of the acrylate resin obtained in Example 23 was treated in the samemanner as in Example 27, to obtain a development pattern of aresin-cured product in which only non-exposed portions were dissolved inmethyl ethyl ketone. A pencil mar strength (JIS K5400) of theresin-cured product was B.

Comparative Example 17

10 g of bisphenol A ethylene oxide adduct diacrylate (LIGHT-ACRYLATEBP-4EA, supplied by KYOEISHA CHEMICAL Co., LTD.) was degassed and moldedat 100° C. and then cured at 200° C. for 6 hours, to obtain a curedproduct.

The cured products obtained in Examples 24, 25, and 26 and ComparativeExample 17 were evaluated for properties.

Table 10 shows the evaluation results of the physical properties.

TABLE 10 Ex. 24 Ex. 25 Ex. 26 CEx. 17 Tg (° C.) 185 183 186 105dielectric 2.71 2.72 2.72 3.21 constant (1 GHz) dielectric 0.0096 0.01100.0102 0.0302 loss tangent (1 GHz) Ex. = Example, CEX = ComparativeExample

1. An acid-modified epoxy acrylate compound obtained by reacting theepoxy acrylate compound represented by the formula (8),

wherein R13 is a hydrogen atom or a methyl group, —X— is represented bythe formula (2′),

in which R2, R3, R4, R8 and R9 are the same or different and are ahalogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, R5, R6 and R7 are the same or different and are a hydrogen atom,a halogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, Y—O— is represented by the formula (3′),

in which R10 and R11 are the same or different and are a halogen atom oran alkyl group having 6 or less carbon atoms or a phenyl group, R12 andR13 are the same or different and are a hydrogen atom, a halogen atom,an alkyl group having 6 or less carbon atoms or a phenyl group, Z is anorganic group having one or more carbon atoms optionally containing anoxygen atom, and each of c and d is an integer of 0 or 1, provided thatY—O— is an arrangement of one kind of structure defined by the formula(3′) or a random arrangement of at least two kinds of structures definedby the formula (3′), and each of a and b is an integer of 0 to 300,provided that at least either a or b is not 0, R2, R3, R4, R8, R9, R10and R11 in the formula (2′) and the formula (3′) being required not tobe a hydrogen atom and n is an integer of 0 to 10, with a carboxylicacid or a carboxylic acid anhydride.
 2. A curable resin compositioncontaining the epoxy acrylate compound represented by formula (8),

wherein R13 is a hydrogen atom or a methyl group, —X— is represented bythe formula (2′),

in which R2, R3, R4, R8 and R9 are the same or different and are ahalogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, R5, R6 and R7 are the same or different and are a hydrogen atom,a halogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup, Y—O— is represented by the formula (3′),

in which R10 and R11 are the same or different and are a halogen atom oran alkyl group having 6 or less carbon atoms or a phenyl group, R12 andR13 are the same or different and are a hydrogen atom, a halogen atom,an alkyl group having 6 or less carbon atoms or a phenyl group, Z is anorganic group having one or more carbon atoms optionally containing anoxygen atom, and each of c and d is an integer of 0 or 1, provided thatY—O— is an arrangement of one kind of structure defined by the formula(3′) or a random arrangement of at least two kinds of structures definedby the formula (3′), and each of a and b is an integer of 0 to 300,provided that at least either a or b is not 0, R2, R3, R4, R8, R9, R10and R11 in the formula (2′) and the formula (3′) being required not tobe a hydrogen atom and n is an integer of 0 to 10, and the acid-modifiedepoxy acrylate compound obtained by reacting said epoxy acrylatecompound with a carboxylic acid or a carboxylic acid anhydride.
 3. Acured product obtained by curing the curable resin composition of claim2.